THE  USE  OF  SELENIUM  OXYCHLORIDE  AS  A SOLVENT  ON  COAL 


BY 

WILLIAM  ROBERT  KING,  JR. 

B.  S.,  Monmouth  College,  1920 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  MASTER  OF  SCIENCE  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE 
UNIVERSITY  OF  ILLINOIS 
1922 


URBANA,  ILLINOIS 


/3J-a.23  /.4P 


I 92S 

K58 

UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 

^^u_s± 1922 

1 HEREBY  RECOMMEND  THAT  THE  THESIS  PREPARED  UNDER  MY 
SUPERVISION  BY„ . Willi  am  Rob  ert  Kingj  Jr.  

ENTITLED ^ e _U  S6-  af  Sel  enium  asy^ciilo  Fide  

As  a Solvent  on  CoaLt 

BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


Recommendation  concurred  in* 

Committee 

on 

Final  Examination* 


•Required  for  doctor’s  degree  but  not  for  master’s 


50940.1 


Acknowl  edgeraen  t 


llils  Investigation  was  undertaken  at  tiie  suggestion  of 
Dr.  Thomas  E.  Layng,  and  was  carried  out  under  his  direction. 

I wish  to  thank  him  for  the  interest  he  has  shown  in  the 
investigation,  and  to  express  my  appreciation  of  the  very 
helpful  advice  and  criticism  he  has  given  at  all  times. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/detaiis/useofseleniumoxyOOking 


Table  of  contents 


Page 


I*  Introduction. 


1.  General  Nature  of  U)al  Solvait  Probl^ 1 

2.  Historical  and.  Theoretical  3 

3.  The  Purpose  of  tlie  Present  Investigation  It 

II.  Es})erimen tal.  Part  I. 

1.  The  Nature  of  Selenium  oxychloride 13 

2.  The  Type  of  Coal  Used 16 

3.  The  Use  of  a Neutral  Solvent  mth  Selenium  oxy dilorlde. 

1*.  Selection  of  the  Neutral  Solvoit 17 

2\  iipparatus  and.  Proceedure 19 

3’,  Examination  of  Products  and  -Analysis 23 

4’.  Oaihoni zation  of  Residues  27 


III.  Results,  Part  I. 

1.  The  Nature  of  Selenium  oxychloride  

2.  The  Action  of  Xylene-Selenium  oxydilorlde  mixture 


on  Co  al  . . 29 

3.  The  Carbonization  of  Residues 32 

IV.  Conclusions,  Part  I 33 

V.  Experimental,  Part  II. 


I.  The  Effect  of  the  Tar  and  Volatile  Content  of  Coal  upon 


the  Resulting  Action  of  Selenium  o:^ chloride  34 

2.  Effi ci Qit  Methods  of  Handling  Selenium  oxychloride  •••  36 

3.  Extraction  of  Coal  with  Selenium  oxy chloriLde. 

1*.  Apparatus  and  Pro ceedure 3? 

2*.  Examination  of  Products  and  Analysis  39 

4.  The  Effect  of  Selenium  oxydrloride  Upon  the  Primary 

Vol atil e Pr’odu cts  of  the  Carbonization  of  Coal  .... 

1*.  Outline  of  Investigation  43 

2 * • App  aratu  s 45 

3\  Temperature  Control  and  Measurement 46 

Proceedure  46 

5*.  0e termination  of  Products  and  Analysis 48 


VI.  Results,  Part  II. 


1.  The  Effect  of  the  Tar  and  Volatile  Contoit  of  Coal 

Upon  the  Resulting  Action  of  Selenium  oxychloride  • 49 

2.  The  Effect  of  Selenium  o:^ chloride  Upon  Coal  50 

3.  The  Pri.mary  Volatile  Pm  ducts  of  Coal  53 

4.  The  Effect  of  Selenium-  oxychloride  Upon  the  Primary 

Vol atil ePmductsofCoal  78 

VEI • Con clu Sion s.  Part  II . 81 

VEII.  Summary  83 

IX.  Bibliograiihy  85 


1 


THE  USE  OF  SELENIUM  OXyaiLORIDE 
AS  A SOLVENT  ON  COAL. 

I*  Introcti ction* 

1.  Gaieral  Nature  of  Coal  Solvent  Problem: 

Uils  investigation  was  tak^  up  as  part  of  a group  of  prob- 
lans  being  studied  in  tliis  laboratory  involving  numerous  so-called 
solvents  and  reagents  such  as  Benzene  and  Xylene  under  pressure, 
mphenyl.  Biphenyl  ether,  and  Selenium  oxychloride*  Ihe  powerful 
corrosive  and  solvent  action  of  selenium  oxychloride  has  been 
known  for  several  years,  in  fact  it  has  beoi  called  by  some  ” the 
uni  versal  sol  ven  t”  • 

Ihe  ^estion  of  coal  solvents  aix)se  during  the  middle  of  the 
last  caitury  and  has  attained  much  prominoice  in  the  past  decade 
until  tod^  the  use  of  solvents  is  recognized  as  one  of  the  four 
chief  methods  of  attacking  coal*  It  has  long  been  realized  that 
tlie  results  obtained  from  ordinary  metJiods  of  analysis,  such  as 
proximate  and  ultimate,  are  of  rather  narrow  application  especially 
from  a chemists  point  of  view*  The  information  derived  from  such 
analysis  is  rather  for  the  engineer*  It  is  such  information  vhich 
can  be  applied  to  engineering  problems  connected  with  the  handling 
and  use  of  coal  such  as  purcJiase,  storage,  weath ering,  coking  and 
ordinary  combustion*  These  analyses  give  percentage  results  of  the 
individual  elements  obtained  by  the  destructive  analysis  of  the 
coal,  but  they  do  not  convey  the  slightest  information  relative  to 
the  actual  organic  constituents  of  coal  as  th^  occur  in  nature. 

It  is  not  witfi  percentages  of  hydrogai,  carbon  and  oxygen  or  their 
compounds  as  produced  by  coking  conditions  and  destructive  analy- 


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sis  that  the  chesnist  is  fundamentally  concerned,  but  with  the  unal- 
tered compounds  in  coal  as  th^  occur  in  nature.  It  is  with  these 
constituents  that  the  ultimate  solution  of  such  problems  as  di still* 
ti on,  combustion,  carbonization, o 2d. da tion,  weatliering  and  storage  lies. 
Here  lies  the  field  for  microscopical  and  solvoit  woiic,  particular- 
ly for  solvents.  If  the  coal  conglomerate  or  any  considerable  part 
of  it  were  to  show  preferential  solubility  in  any  given  liquid  sol- 
vent t?ie  chemist’s  probl^  would  be  greatly  simplified. 

ihe  question  of  vhat  kind  of  a solvent  is  most  desired  by  chem- 
ists is  hard  to  answer.  A true  solven  t,  as  distinct  from  a reagoit, 
sjiould  be  chemically  inert  toward  both  the  substance  extracted  and 
the  residue.  A solvent  is  wanted  that  will  remove  some  part  of  coal, 
it  matters  not  at,  Mi  ether  it  be  cellule  sic,  resent  c,  protein  or 

waxes.  Selective  solvents  are  desired.  lUrthemore  the  coal  consti- 
tuents must  be  removed  unchanged.  Many  so-called  solvents  largely 
used  in  recent  years,  such  as  phenol  and  pyridine,  are  open  to  the 
suspicion  that  results  obtained  by  their  use  have  been  rather  more 
than  that  due  to  a solvent  action  alone.  Ihe  admitted  difficulty 
then  with  most  solvents  is  that  th^  are  reagoits  also. 

There  is  yet  a broader  and  more  practical  field  for  solvents. 
Thus  far  woik:  with  solvents  on  coal  has  not  been  of  very  great  val- 
ue relating  to  carbonization  processes  audit  is  to  this  end,  that 
of  practical  application,  tliat  all  coal  problems  Miould  point. 
Solvents  have  been  used  more  to  leam  of  the  composition  of  coal 
tfian  to  aid  in  the  coking  of  it.  It  is  very  hard  to  link  solvent 
wo  lie  with  carbonization.  From  the  standpoint  of  carbonization  it  is 
the  coking  and  non -coking  const! tuQits  of  coal  Miich  should  be  sep- 
arated. Phenol  and  pyridine  have  been  largely  used  in  this  attempt. 


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but  it  is  doubtful  if  th^  have  proved  the  right  solvents  for  this 
purpose*  To  some  extoit  tJiey  have  proved  successful  as  pointed  out 
by  Jones  and  \iheeler  (1)  (1914).  Generally  speaking  however  there 
has  not  yet  been  found  a solvent  Tihicii  will  seperate  out  the  coking 
from  the  non -coking  constituent. 

2.  Historical  and  theoretical! 

A resume  of  the  leading  woric  ^idtli  coal  solvoits  and  reagents 
follows. 

ue  Marsilly  (18G2)  (3)  made  vhat  is  probably  the  first  compre- 
hensive stutfy  of  solvent  action  on  coal.  He  treated  various  types 
of  coal  witii  al  cohol,  ether,  caibon  disulphide, benzene  and  chlorofom 
at  their  boiling  points.  He  noted  that  all  except  alcohol  had  a dis- 
tinct solvent  action  on  ” f at”  bituminous  coals,  dhloroform  having 
the  most.  Anthracite  coals  were  not  affected  by  these  solvents. The 
treatment  of  good  coking  coals  took  away  some  of  tlie  coking  property 

Guignet  (1879)  (4)  used  dry  phenol  at  110  ’ and  found  that  it 
was  abetter  solvent  for  finely  ground  bituminous  coal  tlian  was 
dilorofonn.  The  phoiolic  extract  was  a deep  brown  color  and  deposit- 
ed brown  flakes  on  cooling.  Four  percent  of  the  coal  was  extracted. 

Don  do  rff,  according  to  Mu<ic  (1881)  (5)  extracted  as  high  as  0.3 
percent  of  some  Westphalian  gas  coals  with  ether.  The  etherial  sol- 
ution was  at  first  fluorescoit  and  after  evaporation  tiie  extracted 
” resin"  was  not  again  Qitirely  soluble  in  ether.  Analysis  of  the 
extract  s3iowed  in  percent:  C - 87.22J  H - 9.2j  0 - 2. 29jt>  - 1.29. 

iteinscii  (1885)  (6  ) took  the  view  that  coal  was  composed  of  two 
substances  iVhich  could  be  distinguished  by  action  toward  certain 
solutions.  With  alkaline  solutions  he  isolated  several  SLib stances 
vhich  were  not  attacked  by  mineral  adds. 


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Siepmann  (1S91)  (7)  made  an  important  study  of  Westphalian  co^ 
by  extraction  with  (hlorofonn  in  a Soviet  extractor.  He  obtained  a 
deei3  brov/ti  solution  with  a green  fluo resell ce.  1111  e extract  equaled 
1.25^  of  the  coal.  It  was  a heavy,  darls:  brown  solid  with  an  odor  like 
petroleum.  He  dissolved  parts  of  the  extract  in  ether,  al cohol  and 
chloroform.  He  also  tried  ether,  al  cohol  and  chloroform  on  fresh 


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C« 

1 

H. 

0. 

N. 

S. 

0 rigin al  coal 

80. 

31 

5. 

, 5 

12 

!.94 

1.  25 

Composite  chloroform  extract 

8 3. 

46 

7. 

,93 

4. 

27 

2.7 

1.63 

Crude  ether  extract  ....... 

84. 

82 

H). 

, 51 

4. 

G7 

- 

- 

Hedissolved  ether  extract  . 

78. 

74 

9. 

,64 

11. 

60 

- 

- 

Al  cohol  extract  ........... 

7 2. 

52 

10, 

,08 

17. 

40 

- 

- 

Uiloroform  extract 

78. 

82 

8, 

, 56 

0. 

97 

- 

2.6  5 

i?inal  coal  residie 

74. 

00 

4, 

,77 

20 

.09 

1. 14 

Watson  Smith  (1891)  (S  ) tested  the  solubility  of  several  csBin^ 
coals  and  a bituminous  coal  from  Miiki, Japan,  in  benzene.  Not  more 
than  one  percoit  extraction  was  obtained  from  any  of  the  cannels, 
but  in  the  Mikke  coal  he  got  a tea  percent  extraction.  He  called  the 
soluble  extract  ” so lubl e bitumen”  or  petroleum.  Ihe  extracted  sub- 
staiice  contained  pyridine  bases  and  phenol  as  well  as  hydro carlDons 
of  the  benzene  series. 

Mderson  (1897  ) (9)  treated  some  Scottish  coals  with  gasoline 
and  with  carbon  disulphide  in  the  cold.  He  obtained  results  similar 
to  Siepmann, but  in  contradiction  to  ue  Marsilly  he  noted  no  differ- 
ence in  the  coking  properties  of  coal  before  and  after  extraction. 

i?nderson  and  Roberts  ) 1898  (10  ) treated  an  oxidized  or  weatiier- 
ed  Scotch  coal  with  dilute  nitric  adLd  and  potassium  hydroxide.  A 


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number  of  substances  of  acidic  nature  were  extracted.  These  were 
tal^en  to  be  derivatives  of  humic  acid.  In  regard  to  the  coking  pro- 
perly of  a coal  attribute  it  to  a certain  substance  in  the  cosQ. 

Which  will  volatilize  or  decompose  easily.  Ni trogen,  sul fVir,  coking 
constituents  of  organic  complexes,  and  an  all  amounts  of  resoiic 
materials  are  pointed  out  as  being  the  main  substances. 

Baker  (1901)  (11)  extracted  finely  divided  coal  ^vith  pyridine 
in  a Soviet  extractor  for  fifty  hours  at  110 '-190 ’O.  Two  bituminous 
coals  and  an  antj^racite  were  so  treated.  Ihe  anthracite  was  not 
attacked  to  any  d^ree.  One  bituminous  gave  20.4%  extraction,  and 
the  other  11.5%.  Ihe  bituminous  coals  lost  all  or  most  of  their 
coking  properties  after  treatment. 

Bedson  (1908  ) (12)  published  results  of  further  e3q)erimen ts 
with  pyridine  on  gas  coals.  He  showed  that  different  constituoits 
of  coal  contained  various  amounts  of  extractive  material. 

Mderson  and  K aider  son  (1902)  (13)  showed  tJiat  the  amount  of 
volatile  matter  presait  in  residues  from  pyridine  extraction  con- 
tained actually  higher  percents  than  the  original  coal.  Ihey  stated 
that  pyridine  was  the  best  solvent  they  had  yet  used.  The  percentage 
of  0,H,  and  N in  the  extract  was  about  the  same  as  that  in  the  ori- 
ginal coals.  The  coking  properties  of  a poor  coal  could  be  entirely 
removed,  but  was  only  partially  ronoved  from  a strong  coking  coal. 

Lewes  (1912)  (14)  infers  from  this  past  woik  ttiat  from  some 
coals  pyridine  dissolves  everything  but  fixed  carbon  and  the  a^i, 
and  that  the  pyridine  must  attacii  itself  to  some  constituent  of  the 
coal  to  fonn  an  additive  compound  insoluble  in  excess  of  pyridine. 
Lewes  says  ’’The  resin  constituents  condition  the  coking  of  coal 
during  destructive  distillation,  and  th^  are  of  at  least  two  kinds. 


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Ihe  first  easily  oxidi zabl e,  solubl e in  pyridine  and.  saponifialDl e by 
alkalies,  and  "i^hich  on  weathering  is  oxidized,  into  a humus  body  with 
evolution  of  water  and.  carbon  dioxLd.e,  and.  is  responsible  for  tlie 
heating  of  coal  in  storage.  The  second,  class  is  non-oxidi zabl e,no t 
saponified,  by  alkalies,  and  forms  ^vitii  pyridine  a compound  insoluble 
in  excess  of  the  reagent,  and  this  class  may  be  the  hydrocarbons 
fix)m  the  decomposed  resins,  as  tlie  residue  in  ishich  th^  are  presait 
yield  rich  liquid  hydro  carbons,  a tar  and  pitch,  but  not  much  gas.” 
Thus  pyridine  is  not  suitable  for  a solvoit  according  to  Lewes. 

Stopes  and  \Vheeler  (1918  ) (15)  contradict  tfiis  conclusion  of 
Lewes  by  saying  that  the  amount  of  volatile  matter  yielded  depends 
upon  the  temperature,  duration, manner  of  heating,  state  of  division 
and  texture  of  the  coal  sample,  all  of  vhich  extraction  of  coal  witli 
pyridine  greatly  affects.  Ih^  go  on  to  state  tliat  retention  of 
pyridine  by  coal  has  not  yet  been  proven. 

Frazer  and  Hof  fin  an  (1912)  (15)  worked  on  the  constituents  of 
coal  soluble  in  phenol.  Of  all  solvents  investigated  th^  reported 
ph0tiol,pyi:d.dine  and  aniline  as  removing  the  largest  quantities  of 
solubl e materi al . PhenoJ  was  selected  for  special  sturdy.  For  lacJc  of 
contrary  evidence  th^  assume  that  coal  substance  soluble  in  phenol 
is  present  as  such  in  the  coal  itself.  Th^  extracted  in  turn  this 
substance  with  numerous  solvaits  and  reagents  and  believe  that  some 
of  the  substances  isolated  very  closely  approach  pure  compounds.  For 
these  th^  present  molecular  weights  and  0,H,  and  0 analysis  in 
several  cases.  A further  study  issing  pyridine  was  to  be  undertakoi. 

Burgess  and  \ftieeler  (1911)  (17  ) made  a very  thorough  investi- 
gation of  the  solvent  action  of  pyridine  on  coal.  Their  results  led 
to  the  establishment  of  the  very  definite  theory  that  coal  is  com- 


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7 


posed  of  two  partsj  first  hydrogen  yielding  or  cellulosic  constitu- 
ent, and  second  the  paraffin  yielding  material*  Ihey  illustrated 
their  results  by  analyzing  the  gases  given  off  at  different  temper- 
atures in  the  destructive  distillation  of  coal  and  try  to  j^ow  that 
the  paraffin  yielding  or  resenic  constituents  of  coal  break  down 
first.  This  theory  has  later  beei  proved  erroneous  by  numerous  in- 
vestigators, among  \ihom  are- 

Porter  and  Taylor  (1916)  (18)  \iho,  woiiring  for  the  bureau  of 
mines,  carri ed  out  similar  work:  tho  unfortunately  on  weathered  coals. 
Th^  arrrive  at  very  different  conclusions  from  Burgess  and  %eeler. 
'Rieir  resul ts, \flil ch  are  very  accurate  except  for  a few  minor  details 
prove  that  the  cellulosic  material  of  coal  is  the  first  to  decompose 
upon  e^osure  to  heat. 

Pictet  and  Ramseyer  (1911)  (19)  made  a study  of  the  solubility 
of  gas  coals  in  benzene.  They  succeeded  in  isolating  h exahy  dro  flu - 
oraie  ^ich  led  to  the  conclusion  that  coals  contain  among 

other  constituents  polymerized  hydroaromatic  hydro  carbons.  From  tire 
similarity  of  distillation  products  to  fractions  from  petroleum  dis- 
tillation the  authors  conclude  that  coal  and  petroleum  have  a sim- 
il ar  origin. 

Wahl  (1912)  (30)  introduced  an  imp ro vesa en t in  experimental  me- 
ttiods  by  mixing  the  coal  to  be  extracted  witii  some  salt  soluble  in 
water. 

Clark  and  Wheeler  (1912)  (21)  extracted  a bituminous  coal  with 
pyridine  and  tlioi  the  extracted  material  with  chloroform.  They  found 
that  between  30-40^  of  the  pyridine  soluble  material  was  soluble  in 
(Siloroform  or  benzoie.  The  analysis  of  their  different  fractions 
and  of  tire  original  coal  on  the  ash  free  basis  is  as  follows- 


> 


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-Solubl  e- 

-Sol* in  bo 

Carbon 

8 2.9  2 

80*81 

77*  32 

8 5*  33 

Hydrogen 

5*  58 

5*  23 

5*  14 

7*08 

Oxygen 

8*45 

10*40 

14.  23 

4*  56 

Ni  trogen 

1*  35 

2*  14 

2*07 

1*71 

Sulfur 

1*70 

1.42 

1*  21 

132 

ihese  results  are  interesting  from  tlie  standpoint  of  Nitrogoi*  If 
the  investigators  purified  tiie  residue  and  extract  from  pyridine 
and  still  get  more  Nitrogen  than  the  original  coal  contained,  it 
would  seon  as  if  the  solVQit  had  acted  like  a reagent  toward  some 
substance  in  the  coal*  Hybetic  add,  waxes,  and  pure  paraffins  were 
found  upon  attempt  to  identify  original  coal  substances. 

Jones  and  %eeler  (1914)  (22)  obtained  crystals  of  paraffin 
wax  melting  between  53*-59*C*  by  extracting  with  pentane  that  por- 
tion of  the  pyridine  extract  iflhich  was  soluble  in  chloroform* 

Stopes  and  ’>Vheeler  (1918  ) (23)  worked  witii  pyrddine  as  a sol  vest 
and  gave  tlie  following  conclusions*  lhat  an  accurate  quantitative 
determination  of  the  extracted  material  can  be  made  only  if  the  coal 
is  ground  fine  and  if  both  coal  and  pyrddinelis  dry*  Most  of  Ihe  ex- 
tractive material  was  removed  in  twelve  hours  in  a Soshlet  extractor 
Small  portions  continue  to  be  ronoved  during  several  we^cs*  One  dif- 
ficulty met  here  as  with  oitiiier  investigations,  is  that  the  coal, 
extract  and  residue  will  absorb  oaygen  in  spite  of  all  precautions, 
more  slowly  at  low  temperatures  and  faster  at  high  temperatures.  This 
osygesi  forms  in  loose  combination  with  certain  parts  of  the  coal 
material* 

Pictet, Ram s^er  and  Kaiser  (1916)  (24)  extracted  five  and  one- 
half  tons  of  Saare  coal  with  boiling  benzene  for  four  days*  From  ttie 
extract  they  isolated  several  pure  hydrocarbons  both  saturated  and 
un  saturated* 

Cherry  (1919)  (25)  carried  out  a series  of  experiments  to  det- 


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9. 

enoAne  the  part  played  by  o:^g0i.  He  extracted  coal  with  ph^ol. 

Uie  residue  and  extract  were  oxidized  seperately  in  various  amounts 
and  after  mi 3dng  were  submitted  to  carboni zation.H e ^owed  that  the 
residue  or  cellulosic  constituent  has  the  greatest  avidity  for  oxy- 
gen* Ibis  cellulosic  material  if  sufficiently  oxidized  will  entire- 
ly prevent  the  mixture  from  coking.  If  the  extract  or  resihlc  mat- 
erial is  partly  oxidized  the  bonding  properties  are  greatly  weakened 

Parr  and  Hadl^  (1915)  (36)  made  a compr^ensive  stu(fy  of  phen- 
ol as  a solvent  on  coal*  Th^  used  a SoJhlet  extractor  and  extract- 
ed the  coal  in  absence  of  air  by  use  of  a stream  of  carbon  dioxide* 
The  tonperature  of  the  extraction  was  tiiat  of  boiling  toluene.  Their 
results  were;  Uoal  varies  as  to  type  in  the  amount  of  soluble  mater- 
ial. The  higher  volatile  matter  coals  give  the  greatest  extraction* 
Extraction  of  coal  leaves  a residue  ^ihich  will  not  coke.  The  coking 
constituent  is  in  the  extract*  The  residue  and  extract  oxidize 
readily  at  room  temperature, but  most  at  100*0*  The  residue  shows  the 
greatest  avidity  for  o:^gen.  Residue  and  extract  both  show  avidity 
for  water,  the  residue  lowing  the  most* Volatile  matter  detemina- 
tions  show  that  the  extract  contains  more  than  the  residue.Ul  timate 
analysis  of  coal,  residue,  and  extract  saiowed  that  percentages  of 
hydrogen,oxygen,ni trogoa  and  caibon  were  substantially  the  same* 
Destructive  distillation  of  coal,  residue  and  extract  gave  gases  of 
practically  the  same  composition. 

Most  of  ihe  wortc  with  solvents  has  been  in  extracting  parts  of 
coal  soluble  in  organic  solv<aits.  All  solvents  tried  have  been 
neutral  solvents,  reagents,  or  oxidizing  agents*  The  reagents  and 
oxidizing  agents  ciiange  the  coal*  They  dissolve  the  coal  it  is  tme, 
but  destroy  one  part  to  obtain  anotlier*  It  is  dicfflcUlt  to  separate 


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10. 

the  true  solvents  from  the  reagents  in  all  cases. The  following  are 
the  most  widely  used:  h Qizene, gasoline,  ethyl  ether,henzene- toluene 
mixture,naph tlialene,  toluene,  alcohol,  anthracene,  diphenyl,  cresol,low 
boiling  tar  distillates, phenol -toluene  mixture,  and  acetone  all  of 
wliicai  are  considered  more  truly  sol  vent  sj  and  carbon  disulfide, 
chloroform,  sodium  hydroxide,ni tri c add, ferric  chloride,  s el enium 
o^ chi ord.de, pyridine, phenol,  quinoline,  aniline,  sul ftir  dioxide, 
diphenyl  ether,  turp^ tine, ozone  and  potassium  di chromate  ivhich  are 
probably  not  sucJi  true  solvents. 

Fats,  waxes, humi c adds  and  in  general  so-call  ed  ” resinic”  mat- 
erials have  been  separated  from  coal  by  solvent  action.  No  solvent 
has  yet  been  found  for  the  ”cellulosic”  and  protein  parts  of  coal. 
These  terms  are  here  used  in  the  general  sense  current  in  tiie  liter- 
ature today  as  originated  by  Prof.V.Lewes  (2)  of  the  University  of 
Manchester  (1911),  to' apply  to  the  two  main  parts  of  coal  as  separ- 
ated by  solvents.  The  ” cellulosic?’  is  the  residue  not  extracted 
and  is  supposed  to  be  a d^redation  product  of  cellulose.  The 
"resinitf*  is  the  extracted  material  lahich  contains  the  coal  resins. 
Since  it  is  believed  by  some  that  gum  or  fossil  resins  are  not  a 
true  constituent  of  coal  it  might  be  said  that  su(h  solvents  as 
phenol  and  pyrddine, iihidi  extract  this  part,attack  only  a non -coal 
part  and  hence  the  true  solvent  for  coal  has  not  yet  been  found. 
%ain,  if  nitrogei  and  sulfUr,  that  is  the  proteins,  are  present  in 
both  the  cellule  sic  and  resinic  parts  of  coal  either  tiie  solvents 
used  have  not  been  the  right  ones  or  else  the  protein  was  decompos- 
ed and  scattered  since  the  resinic  extracts  show  no  protein  content. 

Ibus  it  is  seen  that  much  of  the  work  with  solvoits  upon  coal 
has  led  to  the  very  generally  accepted  throry  that  the  organic  con- 


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11. 

stituents  of  coal  fall  into  two  classes,  the  cellulosic  and  the 
resinic.  Ihe  resinic  type  is  tliat  claimed  to  he  present  in  the  ex- 
tractive matter, \ihil e the  cellulosic  is  found  in  the  residue.  This 
general  hypothesis  has  heen  substantiated  hy  numerous  investigators 
using  various  solvoits.  A very  plaisible  interpretation  of  this 
theory  may  be  stated  in  a slightly  differoit  way,  ?hich  may  give  a 
new  aspect  to  the  subject.  According  to  various  wort  done  on  the 
constitution  of  coal  it  may  be  said  that  there  are  two  kinds  of 
resins  in  coal,  the  original  gum  or  fossil  resins  afdthe  plants, 
and  a d^redation  resin  product  of  cellulose  or  the  cellulosic  res- 
ins.Ihe  extractive  matter  from  coal  generally  termed  ” resini c” may 
thfti  be  thought  of  as  containing  both  cellulosic  resins  and  plant 
resins  principally  the  former,  i^ile  the  cellulosic  "residue”  con- 
sists of  tme  cellulose  plus  cellulosic  degredation  products. 
Thiessen  (28)  in  his  microscopical  study  of  coal, bears  out  this 
view  in  the  discovery  of  more  triily  plant  resins  in  the  "attrdtal" 
material,  and  the  cellulosic  resin  or  ” an tli ration”  material  ^ihich 
he  claims  has  passed  through  a hydrogell  stage.  The  cellulosic  res- 
ins may  be  tJiought  of  as  forming  the  large  part  of  tJie  bonding  mat- 
erial for  coke, vSiile  ttie  plant  resins  yield  the  paraffins  and  tar. 
Solvaits  used  so  far  have  in  general  extracted  the  resins  asa  class 
without  making  any  selective  distinction  between  the  types.  Whether 
the  action  of  seloiium  o^ chloride  would  throw  any  light  on  this 
question  was  doubtful,  but  at  least  some  action  dividing  the  coal 
into  an  extract  and  a residue  were  expected* 

3.  The  Purpose  of  the  Present  Investigation: 

The  purpose  of  this  investigation  was  primarily  to  study  the 
action  of  Seleiium  oxychloride  on  coal, in  parti cul ar,i ts  action  as 


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a solvent.  Hie  prol)lem  is  a new  one  in  so  far  as  a study  of  the 
literature  shows.  Not  a great  deal  is  laiown  about  tiie  action  of 
selenium  oxychloride  as  it  is  one  of  tlie  newer  compounds,  and  as  tiie 
reagent  is  not  plentiful  on  the  maricet.  Literature  on  selenium  oxy- 
(Siloride  is  limited  to  a few  brief  articles  and  to  one  brief  moi- 
tion  of  its  action  on  coal.  Hie  wort  referred  to  is  by  Prof. V.Lenh er 
(27)  \\4io  is  perhaps  the  best  authority  on  sel^ium  oxaichloride  in 
^erica.  He  reports  the  folloiving  results  from  treatment  of  various 
types  of  coal  with  the  reagent: 

With  natural  coals  the  bitumen  is  extracted  leaving  a carbon- 
aceous residue.  Mthracite  coal  containing  little  vol atil e matter 
1^0 ws  little  action.  Semi -anthracites  lose  considerable  amounts  of 
extractive  matter.  Illinois,Ohio,  cannel,  and  bituminous  coals  from 
Pennsylvania  and  Virginia  lose  a large  amount  of  extractive  matter. 
Hie  insoluble  residue  was  found  to  contain  selenium  and  (hlorine. 
With  powdered  coals  seloiium  osy chloride  reacts  evolving  heat. 
Hiorxiughly  ignited  coke  loses  nothing. 

With  tJiese  points  in  mind  and  remembering  tlie  extremely  re- 
active nature  of  the  solvent  and  the  difficulty  ivith  ishich  it  may  be 
handled  the  present  work  was  begun.  It  was  decided  to  confine  tlie 
investigation  to  one  representative  coal.  With  no  preddeit  as  a 
basis  upon  ^ich  to  b^in  worh  the  following  general  points  were 
laid  down  as  a basis  uiion  vhich  to  conduct  the  investigation: 

1-  To  ascertain  the  nature  of  selenium  o:^d[iloride  for  the  purpose 
of  classifying  it  as  a solvent  or  a reagent. 

2-  To  determine  the  most  efficient  method  of  handling  it  in  con- 
nection dlh  coal  solvent  work. 

3-  To  observe  the  effect  of  sel^iium  oxychlordde  upon  coal  both 


13. 

physically  and  chemically. 

4-  To  observe  ttie  effect  of  the  solvent  upon  any  substances 
knowi  to  be  in  coal, or  formed  from  coal  by  such  processes  as  des- 
tructive distillation  and  carbonization. 

5-  To  note  any  oxidation  effect. 

6-  To  attoapt  to  separate  unchanged  one  or  more  fundamental  parts 
of  coal. 

7-  To  distinguish  if  possible  betiveen  the  various  types  of 
resinic  material  in  coal. 

II*  E^erimaital,  Part  I. 

1*  The  Nature  of  Selenium  o^ chloride: 

Only  very  pure  selenium  oxychloride  can  be  used  in  solvoit  \vork 
The  solvait  hydrolyzes  very  easily  and  must  be  protected  from  mois- 
ture and  even  from  long  exposure  to  the  air  of  the  laboratory.  There 
are  three  metJiods  used  in  manufacturing  the  solvent,but  without  spec||* 
i al  app  aratu  s i t i s very  di  f fi  cul  t to  tu  m ou  t a pu  re  p ro  du  ct  an  d 
protect  it  from  hydrolysis  while  making*  Hydrolysis  throws  out  the 
red,  anorphou s form  of  selenium  and  converts  the  oxychloirLde  into  the 
acid.  Because  of  the  e^DOise  connected  with  the  purchase  of  tire  re- 
ag^t  careful  use  of  rather  anall  quantities  was  necessary.lt  was 
found  however,  that  accurate  results  may  be  obtained  from  use  of 
an  all  portions  of  the  solvent  provided  a reasonable  proportion  of 
coal  is  taken*  Surplus  of  selenium  o3gr chloride  present  during  ex- 
traction does  not  materially  change  the  results  of  its  action  on  a 
given  quantity  of  coal. 

The  highly  reactive  nature  of  selenium  o^cJiloride  is  estab- 
lished by  a study  of  its  chemical  and  physical  properties,  and  tiiere 


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14 


is  little  need  of  confinnatory  evid^ce  through  use  of  it  on  coal  to 
place  it  in  Hi e list  of  strongly  reactive  chemicals.  The  reagent  is 
a liquid,  slightly  yellow  in  color  as  ordinarily  prepared.  Its  boil- 
ing point  is  variously  givai  at  from  175*-179  *0.1he  reagent  dissolv- 
es with  ease  such  non*^netals  as  members  of  the  sulfhr  family.  There 
is  an  e:q>losion  \ri.th  such  substances  as  ihite  pho sphorou s,po tassium, 
turpentine,  and  sometimes  with  un saturated  hydrocarbons. The  halogens 
are  dissolved,  carbon  in  form  of  graphite,  charcoal,  activated  dharco^ 
and  the  diamond  are  not  attaiSced  in  the  cold.Practically  all  metals 
are  attached,more  rapidly  at  higher  temperatures,  to  give  the  chlo- 
ride of  the  metal  and  red-brovm  mono  chloride  of  selenium.  Carbona- 
tes of  Na,K,  Sr,  Zr,  react  with  liberation  of  U)2*0ther  carbonates  are 
attacked  slowly .N atural  asphal  ts,  resins,  and  bi  turn en  dissolve  ^vith 
ease  in  the  cold  #ien  they  are  of  un  saturated  diaracter.  Gums,  resins 
paints, lacquer,  celluloid  and  glues  di ssolve. In solubl e phenol! c con- 
dQisation  products  such  as  bak elite  dissolve  readily. Vegetabl e and 
fish  oils  form  a rubber  like  mass. Protein  materials  dissolve  more 
readily  ^en  heated.  With  carbohydrates,  cellulo se  is  not  attacked. 
Starch  and  sugars  are  decomposed  vhen  heated. All  forms  of  rubber 
react  chemically  in  the  cold.  The  chemical  (haracter  of  the  rubber 
is  (hanged.  The  more  <x)mmon  sulfides  react.  Most  oxidizing  agents 
dissolve. 

The  action  of  selenium  oxjr(3ilorlde  upon  the  hydrocarbons  is  of 
spedal  interest.  Saturated  aliphatics  such  as  decane, pentane,  and 
hexane  are  non  misdble,  the  hydrocarbon  floats  on  top  of  the  reag- 
ent. The  paraffins  are  very  slowly  attached  at  high  temperatures. 

Un  saturated  hydrb  carbons  unite  directly.  The  heavier  paraffins  such 

as  vaseline  and  paraffin  float  on  top  of  the  reagent, but  vhen  heat- 
ed to  150  *-150  *C.  tlie  two  become  miscible  until  cool.  Aromatic 


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15. 


hydrocartDons  such  as  h enzene,  tolu ene  and  3^1  ene  make  perfect  sol- 
utions. It  has  long  been  accepted  that  there  was  no  reaction  with 
these  hydro  carbons,  and  it  is  doubtful  if  any  action  does  take  place 
under  thirty  hours.  This  will  be  considered  more  at  length  later  in 
the  text.  Benzene  and  toluene  from  physical  mixtures  vhich  can  be 
separated  by  physical  means  such  as  fractional  distillation.  The 
complete  recovery  of  the  hydrocarbon  can  also  be  accompli ^ed  by 
hydrolysis  of  the  selenium  o:^ chloride  with  water.  The  separation 
of  hydrocarbons  may  be  made  by  enploying  selenium  oxychloride. 
Saturated  paraffins  may  be  separated  from  un saturated,  and  aliphatic 
from  aromatic.  Ihe  aromatic  form  a solution  while  the  lighter  ali- 
phatic rises  to  the  top  forming  an  immiscible  layer. 

Chloroform,  carbon  tetrachlo ride,  carbon  disulfide  and  benzene 
are  good  solvents  for  sel^ium  oxychloride.  The  same  care  must  be 
taken  in  tlie  laboratory  with  this  reagent  as  with  any  other  highly 
corrosive  liquid.  Vapors  inhaled  hydrolyze  with  the  muc»us  membrane 
of  the  throat  and  nose  forming  hydrochloric  add  with  an  irritating 
result.  Phosgene  is  readily  formed  by  decomposition  of  selenium 
oxychloride.  This  poisonous  gas  togetlier  with  moisture  are  the  two 
main  things  to  guard  against.  As  has  been  stated,  water,  al  cohol,  and 
moist  air  of  the  laboratory  will  hydrolyze  the  reagent.  Utmost  pre- 
cautions must  be  taken  to  have  all  apparatus  and  materials  clean  and 
absolutely  dry.  Since  selenium  o:^ chloride  is  add  in  nature  moisture 
forms  selenous  add  and  gives  off  HCL  fUmes  with  the  attoidant  pre- 
dpitation  of  red  selenium.  Cork  stoppers  are  as  impossible  of  use 
as  are  rubber.  Th^  are  slowly  dissolved  by  the  ftimes  of  the  reagent 
Dry  ether  is  misdble  in  all  propoBtions.  Keroseie  and  gasoline  are 

largely  immisdble  in  the  cold.  The  kerosoie  gradually  becomes  dis- 
colored. 


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16 


2*  The  lype  of  Coal  Used: 

For  this  investigation  a high  grade,low  sulfur  Illinois  Bitum- 
inous coal  was  used.  The  coal  is  a fairly  good  coking  coal  from 
from  Franklin  county  going  under  the  trade  name  of  Makitan,and  is 
very  representative  of  the  better  class  of  Illinois  coals.  A large 
supply  of  fre^  coal  was  obtained  and  stored  in  size  large  enough 
to  prevent  rapid  weathering.  A portion  for  analysis  was  ground  to 
60  mesh  after  air  drying,  and  the  follo^idng  complete  proximate  and 
ultimate  analysis  made  upon  the  Air  dry  basis.  Percentages  were 
computed  to  other  bases  as  indicated. 


Analysis  for: 

As  Rec*d. 

Air  dry. 

Dry. 

Combustibl 

Air  dry  loss 

3.0  5 

Moi  sture 

6.28 

3.  33 

- 

- 

Volatile  matter 

33.  21 

34.36 

35,  42 

39.08 

Ash 

8.74 

9.02 

9.  33 

- 

Fixed  Carbon 

51.77 

53.  39 

55.  25 

60.92 

To  tal  Carbon 

69.93 

7 2. 17 

74.62 

8 2.40 

SulfUi' 

0.998 

1.02 

1.0  54 

Nitrogen 

1.45 

1.  50 

1.  55 

Osygen 

8.011 

8.24 

8 . 55 

Hydrogen 

4.601 

4.7  2 

4.90 

B.T.U. 

12,  451 

12,8  43 

13,  280 

Unit  coal 

14,810 

The  analytical 

wo  rk  was 

carried  out 

along 

the  lines  a 

used  by  the  i/Lvision  of  Applied  Chemistry  in  coal,gas,oil  and  other 
fuel  analysis.  Ihe  Total  oarbon  vias  deterniined  in  a Parr  Total 
Carbon  appai^atus.  The  SulfUr  by  the  Parr  standard  sodium  peroxide 
method.  The  Nitrogen  by  the  Kj  el dahl -Gunning  method.  The  Hydrogen 


1 


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and  Oigrgen  were  calculated  by  use  of  Dulong’s  fomula  excluding 
moisture  according  to  the  Uni^cersity  of  Illinois  method*  This 
method  has  i^own  exactness  better  even  than  the  ordinary  combustion 
methods.  The  calorific  values  were  determined  in  the  Parr  Oxygen  and 
the  Parr  Standard  calorimeters,  several  checfe  runs  being  made  in  each 
The  unit  coal  value  was  calculated  according  to  the  Parr  formula. 
These  methods  were  used  throughout  the  investigation  \i4ieneTeer  anal- 
ysis was  required.  Any  deviation  from  the  standard  methods  will  be 
pointed  out  Tihoi  used. 

3.  Th e U se  of  a Neutral  Solvent  vdth  Selenium  Osychlord.de: 

1*.  Selection  of  the  Neutral  solvent: 

In  some  lines  of  work  with  selenium  oxychloride,  such  as  tiie 
separation  of  metals,  a diluting  agent  like  ailphurdc  add  is  used  to 
advantage  to  lessen  tire  powerfhl  action  of  the  selenium  oxychloride. 
This  method  of  handling  the  reagent  was  first  applied  to  the  present 
investigation  on  coal.  An  attempt  was  therefore  ma.de  to  find  a sat- 
isfactory neutral  solvent  to  use  as  a dilutant  for  selenium  oxychlo- 
rd.de.  Such  a substance  must  be  a liquid  and  must  have  no  solvent 
action  itself  upon  the  coal, nor  react  in  any  way  with  the  selenium 
o ^ chi  o rd  de.  I f su  ch  a sub  s tan  ce  coul  d b e foun  d i t v/as  in  ten  ded  to 
use  it  with  the  selenium  oxychloride  in  various  concentrations 
thus  obtaining  selective  solvent  action  upon  the  coal.  At  the  begin- 
ning of  Ihe  investigation  it  was  thought  that  pure  selenium  oxychlo- 
rdde  itself  alone  would  have  too  great  an  effect  upon  the  coal, pro- 
bably dissolving  most  of  the  coal  and  preventing  any  separation  of 
extract  and  residue. 

After  studying  Ihe  action  of  selenium  oxychloride  with  vardous 
Substances  it  was  found  tliat  the  aromatic  hydrocarbons  benzene. 


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18. 

toluene  and  sylene  answered  the  requirements  most  fUlly.  Hiey  are 
miscihle  in  all  proportions  ^vith  the  reagoit  with  which  they  are 
not  supposed  to  react*  Two  extractions  of  fresh  coal  were  made  with 
each  of  these  hydrocarbons  to  detennine  which  had  the  least  solvent 
action  upon  the  coal*  Five  grams  of  co al , after  h eing  dried  at  105’ 
for  an  hour,  were  extracted  ^vith  70 cc*  of  Ihe  hydrocarbon  in  a sox- 
hlet  extractor  for  seven  hours  at  the  boiling  temperature  of  the 
hydrocarbon*  The  temperature  of  extraction  varied  of  course  with  the 
hydrocarbon  used,  and  the  time  allowed  was  sufficient  to  allow  for 
complete  extraction  since  maximum  reailts  were  desired*  Upon  com- 
pletion of  the  extraction  period  the  coal  residue  in  the  cone  was 
wa^ed  for  two  hours  with  9 5^  ethyl  alcohol  to  ronove  the  hydro- 
carbon, said  then  with  ethyl  ether  to  wa^  the  residue  free  of  alcohol 
and  leave  the  mass  in  a condition  ready  for  quick  and  complete  dry- 
ing* The  hydrocarbon  extract  solution  together  with  the  alcohol -eth- 
er washings  was  poured  into  a an  all  distilling  flask  and  all  but 
fifteoi  cubic  centimeters  of  the  liquid  mixture  distilled  off*  The 
remaining  liquid  containing  the  extract  was  transfered  to  a sjnall 
weighed  beaker  and  evaporated  to  dryness  on  an  electric  hot  plate* 
The  dry  extract  material  from  all  three  hydro caibons  was  d.ark  brown 
and  rather  gummy* After  drying  the  extract  was  cooled  and  weighed. 

The  gain  in  weight  of  each  weighed  beaker  indicated  the  amount  of 
extraction  from  five  grams  of  coal  by  the  hydrocarbon  solvent  used* 
Percentage  extraction  was  calculated  fix>m  the  weight  of  the  extract 
The  residues  were  removed  from  the  cones  and  dii_ed,  together  vriih  the 
cones,in  an  electric  drying  oven  in  a stream  of  dry  air*  %en  dry 
and  in  equlihrium  \d.th  the  atmosphere  of  the  laboratory  the  resi(Jres 
were  cooled  and  weighed*  Percentage  extraction  was  cal  culated  from 


.1 . 


K 

13 


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the  v/eights  of  the  residue.  In  all  cases  the  percentage  extraction 
as  calculated  from  the  extract  was  much  higher  than  that  calculated 
from  the  dry  residue.  There  is  a possibility  that  the  extracts  were 
not  separated  thoroughly  from,  the  solvent.  Extraction  as  calculated 
from,  the  residue  was  taken  as  more  nearly  correct,  Reail  ts  obtained 
here  closely  check  with  investigation  carried  out  elsewhere  along 
the  same  lines.  Table  I shows  the  average  results  from,  this  test. 

Table  I. 


Solvent 


io  Extraction  ^ Extraction 

(calc.  from,  extract)  (calc,  from  residue) 


Benzene  5.41  2,6  2 

Toluene  3.30  1.77 

Xylene  1,22  0,25 

From  these  results  it  was  concluded  that  :^lene  was  the  best 
neutral  solvent  to  use  \9lth  selenium  oxychloride.  The  ^lene  used 
was  a mixture  of  the  o,m,  and  p xyloies.  The  clear  distillates  of 
the  xyl ene,  al  cohol  and  ether  were  evaporated  and  no  trace  of  coal 
extract  found  in  than. 

2*.  iVpparatus  and.  Proceedure: 

A series  of  ten  extraction  runs  were  made  using  a toi  percent 
solution  of  selenium  oxychloride  and  xylene,  and  varying  the  time 
of  extraction  and  the  temperature.  The  apparatus  used  is  shoivn  in 
Figure  I,  Ten  grams  of  air  dried  coal  were  dried  at  10  5' C.  for  an 
hour  in  an  electirLc  drying  oven.  The  coal  to  be  extracted  w^as  then 
transferred  rapidly  from  the  drying  oven  to  the  extraction  flask(h). 
lOOcc.of  the  solvent  solution  (OOcc.of  xylene  to  10 cc.  sel enium  oxy- 
chloride) were  added  to  the  flask.  The  extraction  flask  was  a 250 cc. 
wide  mouth  pyrex  flagk  with  flat  bottom,  three  inches  in  height  in 


M * ( 


<> 
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20 


the  body  and  measuring  three  and  one-fourth  inches  in  diameter  at 
the  widest  point.  Colic:  stoppers  were  used  and  tJie  flask  connected 
to  an  air  reflux  cx)ndQiser  (i  ) consisting  of  a glass  tube  three  feet 
long  and  one-half  inch  in  diameter.  All  connections  were  sealed  i?ith 
a mixture  of  litharge  and  glycerine.  Dry  nitrogen  free  from  oxygen, 
obtained  by  passing  the  gas  through  the  drying  train  (l,m,  ) was  pass 
ed  into  the  extraction  flask  from  the  nitrogen  reservoir  (n ) at  con- 
stant pressure  for  a time  to  displace  all  air.  During  extraction  a 
slow  stream  of  nitrogen  was  passed  thro  the  apparatus  escaping  thro 
the  air  cxm denser  and  out  the  sulfuric  acid  trap  (j  ).  Contraction 
in  the  flask  was  relieved  by  automatic  taking  in  of  air  thro  the 
alkaline  pyrogallol  trap  (k  ) which  removed  the  ojygen.  The  extrac- 
tion flask  wras  held  upright  in  an  electric  resistance  fUmace  i^own 
in  detail  in  Figure  I,  and  was  ^laken  occasionally  (firing  the  extrac- 
tion, Tonperatu  re  measurement  was  takm  in  this  series  of  runs  wilh 
an  ordinary  mercury  thennome ter,  and  heat  control  was  obtained  by  use 
of  resistance  coils  shorn  in  a later  figure.  The  first  eight  runs 
wrere  made  at  rooro  temperature  and  required  no  use  of  fh mace.  Runs 
9 and  10  were  made  at  100 'C.  the  flask  being  cooled  dovai  to  room 
temperature  in  an  atmosphere  of  nitrogen  after  completing  the  run. 
The  time  of  extraction  of  the  eight  runs  made  at  room  temperaitre 
(20 ’o)  was  varied  from  five  hours  to  137  hours.  Ihe  two  mns  at  100  ’ 
were  of  five  hours  duration.  Very  little  if  any  heat  was  givm  off 
by  action  of  the  solvent  mixture  during  the  extractions  at  room  ton- 
perature.  During  extraction  the  mixture  in  the  flask  was  reddish- 
brown  in  color  and  showed  green  fluorescence. 

After  extraction  the  contents  of  the  flask  were  poured  out  into 
a large  paper  filter  and  the  flask  rinsed  out  with  xylene.  The  res- 
idue on  filter  was  well  washed  with  3ylene  and  the  extract  solution 


^m4 


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22, 


together  Avith  the  2^1  ene  washings  caught  in^^a  lai^e  Erlenmeyer 
flai^.  The  colarr  of  this  extract  solution  after  filtering  was  red~ 
brown, much  darker  -Qian  the  original  solvent  mixture,  and  had  a ratti- 
er oily  app earan ce. Ih e color  of  this  solution  deepened  according  to 
the  iQigth  of  time  and  the  tonperature  of  the  extraction.  Ihe  res- 
idue ivas  next  washed  with  small  portions  of  ether  to  remove  the 
lene.  This  washing  was  continued  until  the  wai^i  liquid  was  fairly 
colorless.  These  ether  washings  were  kept  separate  from  the  extract 
solution.  The  residue  at  this  stage  was  black  with  the  general  ap- 
pearance of  wet  powdered  coal.  It  was  now  transfered  vhile  still  wet 
with  ether  to  a 200 cc. Erl enmey er  flask. Nearly  all  of  the  residue  can 
be  transfered  to  the  flask, but  ev^  with  the  greatest  care  some  is 
lost  on  the  filter  and  during  tlie  repeated  washing  ..pro  cess.  Ihis 
flask  containing  the  residue  was  placed  in  the  electric  ftimace  and 
connected  to  the  nitrogen  drying  train.  Outlet  to  ttie  flask  was 
secured  by  means  of  a small  glass  tube  instead  of  the  reflux  air 
cond^ser.  The  opoi  end  of  this  tube  passed  into  a sulf\irLc  acid 
trap  to  protect  the  drying  flask  from  moisture.  Dry  nitrogen  was 
passed  through  this  drying  flask  over  the  residue, whi ch  was  dried 
for  from  5 to  12  hours  at  a temperature  of  from  200‘-280’u.  Ether 
ftimes  were  bubbled  off  thro  the  sulfUi^c  add  trap  together  with  the 
escaping  nitrogen.  The  flask  v/as  next  cooled  dom  in  this  atmosphere 
of  nitrogen  and  op^.ed,  and  the  residue  now  quite  dry  and  powdery 
was  transfered  immediately  to  a weighed  sample  tube  and  sealed.  The 
coal  residue  thus  cleaned  and  dried,  was  black  and  ^iny,much  like 
the  original  coal  in  app earfaice.  They  had  only  a trace  of  odor  of 
ether  about  them. 


m 


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23, 

3*,  Examination  of  Products  and  ^alysis: 

The  sealed  tubes  containing  the  residues  were  weighed  and  in 
eadi  case  a gain  in  weigh  t,  in  stead  of  a loss,  was  found.B  ecau  se  of 
this  gain  in  weight  it  was  not  possible  to  tell  tSi ether  there  was 
any  loss  due  to  solvit  action  of  the  reagent  upon  the  coal.  Such  a 
gain  in  weight  indicates  that  the  residue  in  all  probability  was 
not  washed  free  of  the  solvents,  and  that  the  selenium  oxychloride 
attadced  or  decomposed  some  part  of  the  cjoal  ^ich  added  on  selen- 
ium. and  thus  added  weight  to  the  residue.  There  is  little  doubt  but 
that  there  is  some  form  of  s el enium,  ei th er  red  or  gray,preseit  in 
the  residues  as  thus  prepared,  Ihe  great  variance  of  gain  in  the 
ten  runs  is  due  to  the  extraction  and  to  the  chemical  action  of  the 
reagent  resulting  in  the  decsom.po si td.on  of  selenium  oaqy thlnride  to 
deposit  selenium  in  the  residues.  In  Table  II,  is  givoi  the  data  on 
these  ten  runs  showing  the  gain  in  weight  of  the  residues  for  the 
given  time  and  t^perature  of  extraction. 

Table  II, 


Run  Temperature 

Time 

Uiying 

Gain 

Percent  gain 

1 

20  'tl. 

5 hrs 

• 5 hrs. 

, 5064 

gnn,  5,06 

2 

N 

11 

6 

,6999 

6.99 

3 

It 

28 

8 

,4878 

4.87 

4 

ft 

30 

12 

,4190 

4. 19 

5 

If 

91 

12 

.8886 

8.88 

6 

11 

69 

11 

,8  200 

8. 20 

7 

11 

116 

11 

,4540 

4.  54 

8 

11 

137 

12 

,7802 

7.80 

9 

mo 

5 

12 

.8868 

8.86 

10 

100 

5 

10 

.4561 

4.  56 

Residue  was 

taliQi 

from  th  e 

seal  ed 

tub  e in  whi  ch  i t h ad  b een 

ept  and 

reweigh  ed. 

A gain 

of  P,PQ,Q5l  grm. 

was  found  probably  due  to 

xLdation 

and  ^sorption  of  moisture.  The 

residue  was  placed  in  an 

extraction  cx>ne  and  extracted  in  a soihlet  apparatus  for  three  and 
one-half  hours  with  70 cc,  of  ether.  The  ether  was  only  slightly 


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t : niU  • 'f  '«f- 


r ' 


’ -T- 


.'  f. 


r I 


1 


■ V ■ 


. :;^ 


-■  Sf\> 

i ( 


24, 


colored  at  llie  endof  the  extraction.  After  drying  in  an  atmosphere 
of  nitrogen  for  six  hours  at  200 'u.  the  residue  was  found  to  have 
lost  0.2589  grm.  or  2.46^.  Ihe  same  residue  was  then  returned  to 
the  soviet  apparatus  and  extracted  with  different  portions  of 
carhon  di sulphide  for  several  hours.  Ihe  carbon  disulphide  turned 
light  brown  very  quicfely.  Red  and  brown  crystals  of  selenium  were 
extracted  from  the  residue  by  the  carbon  diailphide  and  were  throi^ 
out  of  solution  by  the  addition  of  ether  and  cooling. 

'the  ten  residues  from  the  jyl oie-sel enium  o^gr chloride  extract- 
ions were  analyzed  for  moisture,  volatil  e matter,  ash,  fixed  carbon, 
total  carbon  and  sulfhr.  Ihe  results  are  shown  in  Table  III. Per- 
centages are  tabul ated  upon  both  the  air  dry  and  the  ash  free-mois- 
ture  free  bases,and  are  compared  by  a column  of  difference  with  the 
corresponding  results  on  the  original  coal. 

The  extract  solutions  from  the  ^1  ene-sel enium  0 3?y chlorid.e 
extractions  were  examined  as  follows.  The  extract  solution  was  dis- 
tilled at  reduced  pressure  from  a tlaussen  pressure  distilling 
flask.  A clear  yellow  distillate  came  over  betv;een  20*  and  70’C.  Ihis 
distillate  rapidly  turned  light  amber  in  color  and  showed  a yellow- 
green  fluo resell ce.  It  araelled  stix)ngly  of  selenium  oxychloride  and 
vhite  fumes  were  thrown  off  during  most  of  the  di still ati on. Exam- 
ination of  small  portions  of  this  distillate  hy  the  use  of  vrater, 
al  cohol , eth er,H CL,  ammonium  hy dro xide,po  tassium  hyd.ro xide  together 
ivith  various  distillations  and  fractionations  showed  the  distillate 
to  be  composed  of  sylene  and  selenium  oxychloride  together  with  a 
aiall  amount  of  selenlous  acid.  The  color  was  imparted  to  the  dis- 
tillate hy  traces  of  red  selenium  and  a gummy  compound  of  xylene  in 
union  with  decomposition  products  of  selenium  oxychloride. 


' ,T  .’■■■(, -'-7. 


|K  • f 


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t .>■'  ■•  ' ■ thi'r'ti*'  . ^ • ••;'  7 

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■ J-'i  '■  '■  \ J 'r',»  ''' . V?  L r(0  i-VJ.  I fjjy  ■ lil  i 

' ' ■•■'■''■  ' / 

I-‘  ’f\  : '•*  • > r ' V • . it  jr;’/-'  'bt?!’.  it  •O’  r ''  .’O.;mo:'  O.' 

I . * ' ■ _ 1 

■ ■ ir-  • *.  V ':■}  . I*  •;  •.;  •<.,  ii.cn  '*  i!"  «'  *•'>«  ' " I " 'i  o •'t  r fr.-*!!  * r ‘ 

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I ' ' ■ ' 7' ' "’o  'viv^^nM^  t ri\  ' v ' < »» S'  *• 


!!. 


V 


26 


There  remained  In  the  Claussen  flask  a very  dark,  red-hroA^n  mass 
appeared  to  he  a mixture.  Decan tation,hydroly si s and  filter- 
ing finally  separated  the  mass  into  tv;o  parts.  The  largest  portion 
of  the  mass  was  composed  of  a hro^vn,gummy  substance  consisting  of 
the  extracted  material  of  the  coal  in  combination  with  :^lene  and 
decomposition  products  of  selenium  o chloride. Mu di  red  amorphous 
selenium  was  scattered  throughout  this  gummy  substance.  The  other 
part  of  the  residual  mass  consisted  of  gray  selenium  formed  by  tlie 
heating  of  the  precipitated  red  sel  oiium  thro^m  out  during  the  dis- 
tillation process,  ^y  extract  material  fix>m  the  coal  is  com.bined 
in  this  brown -red, gummy  symp,  but  a separation  of  the  extract  from 
the  addition  compound  holding  it  was  found  to  be  impossible.  The 
material  is  very  thick  and  viscous  with  the  same  yellow-green  flu- 
orescence that  colored  the  sylene  di  still  ate. Upon  standing  the 
mixture,  for  such  it  must  be  called,  tends  to  hard^.  %en  heated  the 
mass  gives  off  white  fumes  and  the  odor  of  rotten  radishes  charact- 
eristic of  selenium  compounds  rhen  decomposed  by  heat.  Heating  does 
not  seem  to  evaporate  the  substance  to  any  marked  degree. 

IXiring  examination  of  a large  portion  of  extract  solution  from 
one  of  the  toi  mns  the  solution  was  shaken  with  a large  quantity  of 
water  and,  quite  by  accidoi t,  allo\ired  to  stand  about  thirty  minutes 
before  separating  in  a separatory  fhnnel.  A heavy  cloud  of  ^ite 
crystals  settled  out  in  the  funnel  between  the  water  layer  and  the 
oily  extract-:^! ene  layer  on  top.  The  water  and  the  crop  of  \hite 
crystals  were  drawn  off  and  the  extract  solution  repeatedly  wa^ed 
with  water  until  no  more  of  the  Thite  substance  cjouldbe  obtained. 
The  crystals  proved  to  be  very  pure.  They  were  subjected  to  physi- 
cal and  chQnical  tests  including  qualitative  organic  analysis  and 


\ ' ‘r... 


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ft}  ‘ . • J. 


■:^':  ■:  m-U.m  '1o  i^-iT  •-  m.j?  ■ -.v.rl  :‘>j-  ^..v•  'Hr  '-’f  • ?;•.■ 

■*  ' ' f 'f*  . ■'??  ".!'  vri'tsx'.'' Y rp  jf./ 

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. ’i"'  S'.  b ■ ' •.■’ I wtn 


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x-0  'Y  ; ' ';■• 

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o.r<vi  , • Y. 

% 

1 

1 

*1 

-‘Y* 

\htj-  IV:. 

■ n ■•  -x^Jl  ,-r . 

''i  * 

^ rV a ' ■ 

‘ V ,r  »■  ' ' ' i 

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K' ' < . • * . 'L  » • 

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2? 


were  found  to  be  pure  3^1  ene  selenic  acid,  formed  by  action  of  the 
selenium  o^drlo ride  upon  the  diluting  jgrlaie  in  the  solvit  mixture 
Ibe  ether  washings  of  the  residues  were  examined  and  were  found 
to  centain  ether,  jgrlene,  s el enious  acid,  sel enium  and  the  same  xylene- 
resini c«sel enium  mixture  identified  in  the  extract  solutions. 

After  identification  of  a compound  Are  to  chemical  action  be- 
tween selenium  oxjr chloride  and  xylene  a test  was  made  upon  the  rea- 
goit  to  learn  more  of  its  action  upon  the  aromatic  hydrocarbons. 
E(pal  portions  of  benzene,  toluene  and  rg^lene  in  separate  test  tubes 
were  mixed  with  the  same  amount  of  pure  selenium  osychlorid.e  and  the 
tubes  sealed.  After  fifteen  hours  the  benzene  showed  no  change,  the 
toluene  had  turned  a deep  r^ine  cx)lor,  and  the  xj^loie  hadbecx)me 
entirely  opaque  being  a browniiSi -black  color.  After  three  days  the 
toluene  and  :^lQie  solutions  were  both  quite  black  rvith  a green 
fluorescence  rhile  the  benzene  solution  had  turned,  a faint  yellow. 

At  the  end  of  five  days  the  three  tubes  were  hydrolyzed  with  water. 
Hie  b'enzene  was  the  only  hydrocarbon  of  the  three  \hich  separated 
out  on  top  of  the  v/ater  in  anything  like  its  pure  form.  Hie  other 
two  tubes  :^o wed  heavy  precipitations  of  red  selenium  and  other  s 
signs  of  decomposition. 

4'.  Carbonization  of  Residues: 

In  order  to  obtain  further  indications  as  to  the  action  of 
this  mixed  solvent  upon  coal,  a carbonization  run  was  made  upon  a 
mixed  sample  of  residue  from  the  ten  runs.  Ihe  products  of  carboni- 
zation and  analysis  of  the  gases  yielded  r/ere  the  principle  factors 
under  observation,  ihe  apparatus  for  carbonization  and  the  methods 
of  analysis  used  were  identical  with  those  e3q)lained  in  detail  later 

on  in  the  text,  so  no  further  reference  will  be  made  to  them  at  this 


'o' ft 


r)  f< 


•■•’Im'  'H'<  14.  -I*'!' 


N 1 , 


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i ‘v'. 


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, ( ■ 


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•■ : 

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' i '*.'■?  t ■ '•»  }=;  f<:-.;  ; 1, 

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.•  f :'i  1 -'L  .«  :';  ••.'f  ^ - ^ -. 

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r.  t- 

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■ 

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, ■ • • 

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. -WTf'J ‘f  ..:’!  ■ ■' 


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>»•«•.  -4 


28 


point*  The  data  and  results  of  the  run  are  listed  in  Tatoie  IV* 

There  was  no  sign  of  tar  in  the  tar  trap  or  in  the  retort*  Red  sel- 
aiium  was  scattered  throughout  all  the  apparatus  even  in  the  gas 
holder*  The  gas  generated  or  yielded  hy  the  residue  had  a very  acrid 
odor  causing  extrone  irritation  to  the  nose  and  eyes,  \\hoi  passed 
over  lead  acetate  paper  it  turned  the  paper  hlad^*  Selenium  in  the 
residue  combined  with  hydrogen  of  the  coal  residue  to  form  hydrogen 
selenide*  This  gas  decomposes  in  part  to  give  red  selenium  found 
throughout  the  apparatus*  To  free  the  gas  from  the  poisonous  hydro- 
gen selenide  so  that  it  might  better  be  analyzed,it  was  passed  thro 
three  tubes  of  lead  acetate*  The  gas  free  of  hydrogen  sel enide, whi (ii 
would  have  caused  an  error  in  the  percentage  of  carbon  dioxide,  was 
then  analyzed  in  a U*of  I*Modified  Orsat  apparatus  as  \?ill  be  ex- 
plained later* 

III*  Results, Part  I* 

1*  The  Nature  of  Selenium  oiy (iiloride! 

It  is  evident  ttiat  selenium  0 2y chloride  must  be  r^arded  as  a 
very  highly  active  reagent*  It  is  not  a good  solvoit  in  that  it  is 
impossible  to  secure  a satisfactory  separation  of  extract,  residu e 
and  the  reagent*  Recovery  of  the  reagent  by  hydrolysis,  with  the 
liberation  of  any  extracted  material,  is  not  possible  in  coal  work 
as  it  is  in  the  separation  of  aromatic  hydrocarbons  and  selenium 
oxychloride,  because  of  chemical  reaction  between  the  reagent  and 
coal*  As  prepared  selenium,  oxychloride  is  very  expensive,  too  much 
so  to  allow  of  much  work  \vith  it  commercially  on  coal*  Selenium  is 
however  very  plentiful,  and  ^ould  there  be  a don  and  for  commercial 
use  of  the  reagent,  no  doubt  a cheaper  and  easier  process  of  manu- 
facture could  be  perfected* 


•jg-iWSw'wini 


V ll*  ■ -^.'  tl^i'  ^ i i-*  , :>--■■  -^.'■-./Jl.t— ■..V  » : 

,' >'v;-‘-'V.'.'(?i  ■ ‘ :.v'  r 

•r  T-' 


1 , • ' 

■iV.Lt:  ''>4ii;-/J! 

w ' 

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fit  'T'' 

} n: 

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1 1 ^ **' 

1 ' i ■ ’ '•'  \ ■ 

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29. 

Table  IV. 

Weight  resictie  coked 

30.0  gm.  from  extractions  2,4,8,  and 

10. 

residue 

22.79  = 7 5.96% 

tar 

0.00 

lype  of  residue:  No  sign 

of  coke, powdered  like  original. 

Combined  data 

on  lun: 

Time  Tanperature 

Gas  Volume  Remarlis 

0 ^00" 

RooM 

0 

15 

70 

100 

35 

190 

250  Moisture  on  retort. 

45 

265 

290 

55 

300 

400 

1 00 

330 

575 

1 15 

390 

800 

2 00 

500 

1800 

3 05 

555 

2900 

3 15 

575 

3040 

4 00 

590 

3400 

4 30 

59  5 

3600 

4 55 

60  5 

37  50 

5 45 

615 

39  50 

6 20 

6 25 

4100 

Gas  data: 

Tonperature 

(m  aximum ) 

6 25*C. 

Time  in  hours 

6.33 

Total  gas 

4100  cc.  including  H 280 

Gas  analysis: 

I 

II  Average  Nitrogen  free 

COg 

8.0^ 

7.9%  7.9%  10.7 

02 

5.8 

6.1  5.9  8.1 

C2P4 

0.0 

0.0  0.0  9.0 

0.0 

0.0  0.0  0.0 

«2 

27. 2 

24.9  26.0  35.7 

CO 

7.0 

7.0  7.0  9.5 

CH4 

24.8 

- 24.8  34. 5 

C2P6 

1.2 

1.2  1.5 

”2 

26.0 

27.2  0.0 

2#  The  Action 

of  '^lene- 

Selenium  oxychloride  Mixture  on  Coal: 

From  th  e 

results  ^ovai  in  Table  II.  it  is  not  possible  to 

draw 

any  conclusions  as  to  comparative  amounts  of  extraction  due  to 

the 

1 eng  th  0 f th  e 

extraction 

period  or  to  the  temperature  of  extraction. 

There  is  undoubtedly  more  extraction  of  iiie  coal  at  the  higher 

temp- 

eratures  and  during  the 

runs  of  greatest  duration,  but  the  chemical 

action  of  tiie 

reagent  upon  the  coal  and  the  sylene  varies  to  sucJi  an 

extent  th  at  no 

definite 

quantitative  results  are  possible.  The 

^ I. 

■ ’ a 

i 


■*  * (■  t - ) 


I 


Ft' 


^ i| 

fc 


1- 

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i. 


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1 

f 


i 


30. 

deepening  in  color  of  the  extract  solutions  from  the  runs  of  great- 
est length  would  seem  to  point  to  more  extraction  or  to  greater 
chemical  action# 

Extraction  of  residues  from  the  mixed  solvent  extractions  ^oiirs 
the  presence  in  the  residues  as  prepared  of  selenium  and  also  quite 
a little  extractihle  matter  \ihich  m_ay  belong  to  the  coal  or  may 
have  been  added  to  the  residue  through  the  formation  of  some  jg^lene 
compound. 

Analysis  of  resit^es  gives  only  comparative  results  at  best. 

The  volatile  determinations  left  no  cobe  buttons  ^ihereas  the  origi- 
nal coal  did.  This  is  an  indication  of  the  loss  of  coking  property 
through  extraction.  Tiie  volatile  matter  nhile  burning  off  gave 
evidence  of  chlorine  and  selenium  in  the  residue.  Vol  atil  e matter 
air  dry  i^iows  a loss  in  six  of  the  ten  runs.  The  net  result  for  the 
ten  runs  shows  an  average  loss  of  1.  335^,  On  t^e  pure  coal  basis  the 
volatile  matter  shows  an  average  loss  of  2.22^.  for  the  ten  runs. 

The  a^i  of  the  original  coal  was  light  gray.  All  ash  from  these 
runs  except  run  1 and  2 ^owed  presence  of  selenium  by  their  brown - 
red  color.  Seven  of  the  ten  runs  iShow  a loss  in  ash  on  tlie  air  dry 
basis  for  an  average  of  0.50^ 

Moistures  on  runs  2-10  inclusive  show  an  average  loss  of  2.81^ 
This  loss  in  moisture  is  explained  by  the  treatmoit  of  ttie  residues 
^fliich  excluded  absorption  of  moisture  from  fee  air.  The  moisture 
figures  are  however  not  important  and  may  be  ignored.  The  loss  in 
asii  is  so  anall  as  to  be  within  e^qperimen tal  error.  Provided  fee 
selenium  o:^chloride  did  not  attack  some  inorganic  constituent  of 
the  coal  it  is  safe  to  assume  that  fee  ash  remains  fee  same  after 
treatment  as  in  fee  original  coal# 

Fixed  carbon  air  dry  shows  a gain  in  six  of  the  ten  runs 


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31, 


corresponding  of  course  to  tlie  volatile  loss.  For  the  ten  runs  the 
average  gain  equals  4.48^#  For  a check  it  may  he  seoi  that  the  aver- 
age gain  in  fixed  cathon  approximately  equals  tlie  sum  of  tlie  average 
loss  in  moi sture,  vol atil e matter  and  aiSi.  The  Fixed  caihon  on  pure 
coal  basis  shows  an  average  net  gain  of  l»31°/o» 

The  total  caihon  air  dry  siiows  a loss  in  all  tai  runs  for  an 
average  of  9*6  2fo,  ihis  verifies  tlie  lossin  volatile  matter  aibove. 

It  seems  that  tlie  anall  amount  of  selenium  oxychloride  present  in 
the  solvent  mixture  j|  ten  percQit  ) was  able  to  ronove  carbon  in 
tlie  form  of  un saturated  compounds,  and  it  is  safe  to  assume  that 
there  was  solvent  action  to  the  extent  of  removing  some  un  saturated 
hydrocarbons  and  resinic  material. On  the  pure  coal  basis  tlie  total 
carbon  shows  a loss  in  all  ten  runs  for  an  average  of  13.0  2^  It  is 
interesting  to  note  tJiat  the  amount  of  loss  in  total  carbon  on  this 
basis  increases  with  the  increased  length  of  the  extraction  time 
and  with  the  rise  of  temperature. 

Sulfhr  air  dry  shows  ten  gains  for  an  average  of  2»37%  ex- 
cepting #1  vhich  is  abnormally  high.  Sulfhr  was  determined  here 
dirett  from  the  total  carbon  residues  and  hence  any  selenium  pres- 
ent will  be  determined  with  the  sulfhr.  This  is  an  added  proof  of 
the  presence  of  selenium  in  the  residues. 

From  the  standpoint  of  extracted  material  the  use  of  ijg/’lene  to 
dilute  selenium  oxychloride  is  a failure  since  it  is  impossible  to 
isolate  any  extract  and  because  there  is  more  chemical  reaction  be- 
tween the  xylene  and  the  reagent  tlian  solvent  action  upon  the  cjoal. 
Most  of  the  xylene  can  be  recovered  pure, but  the  selenium  oxycJilo- 
ride  decomposes  th  the  treatment.  The  red  amorphous  form  of  sel- 
enium is  preset  everyT^iere.  It  is  very  probable  that  some  chemical 


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32, 


action  has  taken  place  between  part  of  the  jgrlene  and.  the  selenium 
oxychloride.  The  daricjh eavy  syivip  substance  is  composed  of  red  sel- 
enium together  witli  any  jgrlene  compound  formed  and  any  tar  or  res- 
inic  material  extracted  from  tlie  coal.  From  the  nature  of  the  mat- 
erial it  seems  very  probable  that  some  resinic  material  has  been 
dissolved  out  of  tlie  coal, but  this  can  not  be  isolated  and  identi- 
fied as  such.  The  hard, gray  substance  formed  upon  heating  tlie  ex- 
tract is  the  gray  crystalline  form  of  selenium  A^ich  is  formed  from 
heating  the  red  selenium.  The  red  amorphous  selenium  is  thro^m  out 
from  selenium  oxychloride  every  time  hydrolysis  or  chonical  reaction 
taltes  place.  -Any  subsequent  heating  of  tliis  form  over  150  *C  will  re- 
sult in  the  formation  of  tlie  gray  seloiium  ^^icil  is  not  soluble  in 
carbon  disulphide  as  is  tlie  red  variety. 

Selenium  o:?y chloride  pmb^ly  forms  some  new  compounds  either 
with  the  re^nic  material  of  the  coal,  the  ^yl ene, or  bo th.Un saturat- 
ed hydrocarbons  of  tJie  coal  might  be  attacked,but  there  is  notway 
of  telling  \ihat  the  resulting  compound  would  be. .Any  chonical  reac- 
tion with  aromatic  hydrocarbons  will  result  from  action  upon  xylene 
since  there  are  no  aromatic  hydrocaibons  in  coal  as  su(3i. 

3.  The  Carbonization  of  Residues: 

Very  interesting  results  were  obtained  from  ttie  data  on  the 
carbonization  run  made  on  the  residue  from  the  jyl ene-sel ^ium  oxy- 
chloride solvent,  and  from  the  gas  analysis  of  this  same  run.  There 
are  no  un  saturated  hydro  carbons  or  boizene  in  the  gas  as  analyzed. 
Benzene  in  cxoal  is  formed  from  un  saturated  hydrocarbons.  The  sel- 
enium oxychloride  here  evidently  ronoved  tlie  unsaturated  hydrocarb- 
ons from  the  cjoal,thus  removing  both  un  saturated  aliphatic  and  sat- 
urated aromatics  from  the  gas.  The  carbon  dioxide  in  Table  IV.  may 


"3 

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33 


"be  slightly  high  due  to  the  fact  that  any  hydrogen  selenide  not 
removed  hy  tlie  lead  acetate  train  will  he  ahsorhedhy  the  KOH  along 
\vi  til  tlie  cathon  dioxide,  ihe  hydrogen  also  may  he  low  due  to  the 
loss  of  hydrogen  ifliicii  united  with  selenium  to  form  the  selenide. 

Ihe  most  important  results  of  the  coking  run  is  the  absence  of  tar 
among  the  products,  and  the  absence  of  the  hydrocarbons  from  the 
gas,  as  pointed  out  above. 

IV.  Conclusions,  Part  I. 

No  quantitative  extraction  of  coal  is  possible  ivith  selenium 
o:!^ chloride  as  a solvent  because  of  diemical  action  and  deposition 
of  selenium  vhich  is  difficult  to  remove.  Ihe  presence  of  :^lene 
increases  the  amount  of  chemical  action  and  thus  tlie  amount  of 
selenium  left  in  tire  residue  and  extract.  \Vhen  xylene  is  used  to 
dilute  the  reagent  there  is  more  chemical  action  at  higher  tempera- 
tures and  in  extractions  covering  the  most  time.  Most  of  the  xylene 
can  be  recovered,bu t its  presence  leads  to  greater  decjompo si tlon  of 
the  reagent.  The  most  careful  and  rapid  treahnent  is  necessary  to 
give  a minimum  amount  of  tlie  red  selenium  Miich  upon  heating  turns 
to  the  gray  metallic  variety. 

Xylene  or  any  other  neutralizing  agent  \d.ll  not  work  xf±th  sel- 
enium o^ycailoride  in  coal  researdi  due  to  chemical  action  and  the 
(Complication  of  products.  ^Vhil  e not  successflil  as  a final  method, 
the  use  of  :^lene  will  give  good  preliminary  results  and  indications 
of  \hat  may  be  expected  from  the  use  of  pure  selenium  oiy  carlo  ride  on 
cxral.  This  shows  that  tlie  most  nearly  perfect  neutral  solvents  are 
not  fitted  for  use  as  a dilutant.  If  any  application  of  selenium 
o:^ chloride  is  to  be  made  it  must  be  in  tire  concentrated  fonii  ihich 
will  eliminate  confusing  side  reactions. 


I 

? 


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34, 


SelQiium  oxychloride  reacts  diemically  \vitli  some  part  of  the 
coal  conglomerate.  Chlorination  with  substitution  of  red  selenium 
results.  It  may  be  possible  to  free  the  residue  from  selenium  so  as 
to  obtain  a pure  residue  for  analysis.  The  extracted  materi  al , \Nhi  ch 
is  probably  resinic  in  nature,  enters  into  chemical  combination  ^vith 
the  reagQit  and  no  separation  is  possible.  New  compounds  probably  of 
the  additive  type  are  formed. 

Selenium  oxychloride  unites  with  ::ylene  to  fom  aach  compounds 
as  xylene  selenic  acid. 

Selenium  and  chlorine  are  botii  present  in  resiAies  from  tliis 
method  of  extraction. 

Maly  sis  of  the  residues  ^lows  very  little  action  upon  the  ash 
of  coal, but  a loss  of  carbon  contoit  both  volatile  and  fixed. 

Selenium  oxydiloride  destroys  the  coking  property  of  coal  and 
extracts  tJie  tar  or  tar  forming  constituents  of  the  coal  as  shoAvn 
by  the  direct  carboni zation  run.  The  extracted  material  is  probably 
composed  of  un saturated  hj’^dro carbon s and  resinic  material. 

Hydrogen  selenide  must  be  removed  from  tiie  coke  gas  before 
analysis.  More  efficient  treatment  of  residues  may  give  a residue 
free  from  selenium  and  thus  eliminate  the  H2Se  from  the  resulting 
gas. 

V.  Experimental,  Part  II. 

1.  The  Effect  of  tlie  Tar  and  Volatile  Content  of  Coal  Upon  tJie 
Resulting  Action  of  Selenium  oxychloride: 

It  would  seem  from  the  above  results  that  the  higher  the  per- 
centage of  volatile  matter  and  the  more  tar  or  tar  forming  material 
in  a coal  the  greater  ^vill  be  the  amount  of  extraction  with  selen- 
ium o:^ chloride.  If  this  is  true  coke  ,witii  no  tar  and  very  little 


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35 


volatile  con teai t,  shoul d ^ow  no  extraction,  and  a partially  coked 
coal  residue  should  show  only  a sin  all  amount  of  extraction.  To  test 
these  conclusions  the  following  extractions  were  made  using  pure 
concentrated  selenium  oxychloride. 

One  to  three  gram  samples  of  cxxke  ground  to  30  mesh  were  ^ak€n 
togetlier  'with  a portion  of  tlie  reagent  in  a small  Erlenmeyer  flask 
for  from  fifteen  to  thirty  minutes.  The  flask  was  wanned  a few  times 
The  (Jon tents  of  the  flask  filtered  easily  and  there  was  no  sign  of 
any  reslnic  or  gummy  material  mixed  witli  the  selenium  oxychloride 
^Dhich  filtered  through.  To  the  filtrate,  rather  "black  in  cx)lor,  was 
added  sufficient  water  to  hydrolyze  the  selenium  oxychloride. 

Red  selenium  separated  out  hut  upon  refLl  tering  this  was  the  only 
Tsuhstance  left  upon  the  filter.  The  resirlue  remained  hi  ack  and  in 
the  same  cx>ndition  as  before  extraction. Washing  with  water  removed 
all  tlie  reagent  hut  resulted  in  throwing  out  much  selenium  ^ich 
remained  in  the  residue. 

A fresh  sample  of  air  dried  cxxal  was  kept  in  a small  stoppered 
flask  witli  selenium  oxychloride  for  one  week.  At  tiie  end  of  tiiis 
extraction  period  it  was  found  impossible  'to  filter  off  the  reagent 
or  any  extract  solution.  The  \hole  mass  was  brown -hi  ack  in  color,  mth 
the  consistency  of  a hea-vy  paste. Water  was  added  and  the  mixture 
stirred.  %en  filtered  the  filtrate  was  clear  water  only.  This  show- 
ed that  the  extract  had  undergone  aich  chemical  reaction  as  to  pro- 
duce a gummy  substance  insoluble  in  water.  Alcohol  dissolved  the 
substance  enough  to  allow  filtering.  The  filtrate  was  chocolate  bro^ 
in  color.  The  residue  after  being  treated  with  alcohol  was  blacJc 
with  a slight  brownii^  tinge.  It  showed  traces  of  selenium. 

A coal  sample  was  secured  ^vhicii  had  been  ground  to  GO  me^i,air 
dried,and  partially  coked  up  to  SOO’o  so  that  practically  all  the 


36. 


tar  had  been  distilled  out.Tliis  sample  xvas  treated  \vith  the  reagent 
for  various  lengths  of  time.  The  result  upon  filtering  was  mudi  the 
same  as  with  coke.  The  mixture  filtered  rapidly  and  tlie  filtrate 
showed  no  signs  of  resinic  extract  obtained  from  fresh  coal. 

A saniple  of  fre^i  coal  was  mixed  witli  tlie  reagent  for  a half  Iru 
hour  and  tlie  mixture  then  filtered,  filtration  was  nearly  impossible 
due  to  tlie  thidmess  and  gummy  nature  of  the  solution. 


2.  Effi ci ent  Methods  of  Handling  Selenium  o:^chloride: 

One  of  tlie  most  convenient  and  usefUl  pieces  of  apparatus  made 
use  of  in  solvent  worti,the  soviet  extractor,  was  first  tried  out. 
Aii»  dry  coal  from  ^ich  all  traces  of  moisture  were  furtlier  removed 
by  heating  to  10  5*Ci.  was  used  in  the  extraction  cone,  and  a suffici- 
ent amount  of  selenium  o^g?^ chloride  was  taken  to  allow  proper  oper- 
ation of  tlie  apparatus,  uork  stoppers  were  used  since  they  showed 
less  attack  from  the  reagent  than  rubber.  It  became  evident  almost 
at  once  upon  starting  tlie  extraction  that  this  method  would  be  im- 
possible to  use.  The  reagent  attacked  the  corks  at  once,  dissolving 
thcsn  to  a jelly  in  a few  minutes  at  tlie  tonperature  developed.  The 
ifliole  of  the  selenium  oxychloride  became  a dark  brown  color  showing 
marked  decomposition  of  both  reagent  and  cortc.Some  of  tlie  reagent 
after  refluxing  ran  down  into  the  extraction  cone  and  that  too  was 
dissolved  into  a pulp  in  a few  minutes. 

Another  method  of  refluxing  was  tried. M ordinary  glass  tube 
was  attached  to  a small  fl ai^c,  con taining  the  coal  and  reagent,  to 
serve  as  a cxm  denser.  Here  the  results  were  also  negative.  The  rea- 
gent attacked  the  stoppers  and  was  itself  decomposed  upon  heating. 

!■  ariiied  Iiy  droly  si  3 was  noted  in  tlie  tube  ^here  fhe  air  came  in  con- 
tact ivith  the  reagent. 


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FTx>m  these  attenipts  it  was  evident  that  no  heating  of  the 
reagent  to  anything  near  its  boiling  point  was  advisable  or  possible 
and  also  that  no  refluxing  system  of  extraction  could  be  used. 

3.  Extraction  of  Coal  with  Selenium  oxychloride: 

^paratus  and  Proceedure: 

Bearing  in  mind  the  results  of  the  previous  tests  the  fol leaving 
final  method  was  adopted  as  the  most  efficient  means  of  treating 
coal  v.atl"i  selenium  o^y ctiloride.  Twenty -five  gram  samples  of  coal 
were  weighed  out  and  dried  in  an  electiric  drying  oven  for  an. hour  at 
10  5’C  to  remove  all  moi sture.  When  dry  each  sample  of  c^oal  was  re- 
moved rapidly  and  transferee!  to  a small  Erlenmeyer  fl ask  (300  cc.  )£aid 
suffideiit  selenium  oxychloride  was  poured  in  to  just  give  an  exces 
above  a thin  paste.  The  flasks  were  stoppered  at  once  with  cork  stop- 
pers. The  coal  mass  swelled  a great  deal  and  mucii  heat  v/as  evolved, 
the  flasks  becomihg  too  hot  to  hold.  The  flasks  were  shaken  and  the 
(x>n tents  stirred  from  time  to  time.  Keat  was  ai)plied  by  slight  warm- 
ing on  azi  electric  hot  pi  ate.  The  total  time  of  extraction  varied 
from  thirty  to  forty  minutes.  Preliminary  trials  showed  that  any 
attempt  to  filter  at  this  stage  was  impossible,  so  at  this  point, 
a an  all  qiiantity  of  benzene  was  ad.ded  to  the  flask  and  the  mixture 
well  shalcen  and  stirred.  The  benz^.e  vlll  not  hydrolyze  the  reagait 
or  extract  any  of  the  coal  in  the  presence  of  selenium  oxychloride. 
The  baizene  being  miscible  with  the  reagent  forms  a perfect  filter- 
ing medium  and  tJie  mixture  whoi  poured  into  a suction  filter  dll 
filter  with  ease.  A slight  suction  was  maintained  throughout  tlie 
filtering.  The  contoits  of  the  flask  were  washed  out  into  the  fil- 
ter Ylth  aaall  portions  of  b enzene.  The  filtering  became  slower,but 
vlth  repeated  washing  of  tJie  resicTue  with  benzene  the  process  was 


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38 


completec!.  \d.thout  mucti  loss  of  time  or  hydrolysis  of  selenium  oxy- 
<3ilonL(^e*  Ihe  extract  solution  washlack  and  very  viscous.  It  con- 
tain ed  th  e sel  eniuin  o xy  di  1 o r±  de-b  en  aan  e mi  xtu  re  tog  e th  er  \vi  tli  th  e 
extracted  substance  of  the  coal.  Ped  selenium  rapidly  separates  out 
in  this  extract  solution.  The  solution  was  stoppered  and  set  aside 
for  examination. 

The  resiclue  on  filter  was  washed  vdth  ether  until  all  traces  oi 
benzene  had  been  ronoved  and  the  ether  washings  became  cl  ear.  These 
ether  washings  were  reserved  in  a separate  flask  for  examination. 

The  residue  was  now  scraped  out  onto  a large  filter  paper, 
powdered  with  a spatula  and  allowed  to  dry  partially.  Hie  colro  at 
this  stage  was  black  with  a bro\m  tinge  attributed  to  presence  of 
selQiium.  The  residue  gave  off  a strong  oclor  of  chonicals.  tVhen 
nearly  dry  the  residue  was  transfered  to  a beaker  and  repeatedly 
w’ashed  by  decantation  with  b enzene  until  the  washings  filtered  cleai. 
This  was  to  insure  complete  ronoval  of  any  selenium  oxychloride  and 
extract  remaining  in  the  residue.  WasJiing  in  the  same  manner  ivith 
ether  gave  a fairly  clean  residue  iiiiicJi  was  dried  in  a large  flask 
in  an  atmosphere  of  nitrogOi.  %en  dry  the  residue  was  put  through 
a 60  mesh  screen  and  tlien  fhrther  dried  in  drying  oven  for  two  hour? 
at  from  50 ’-170*0  dry  nitr*ogen  being  passed  tJiro  the  oven.  A residue 
was  thus  secured  practically  free  from  ch emi cal s,  and  bl ack  and  pow- 
dery with  the  same  appearance  as  the  original  cjoal.The  residue  was 
stoppered  in  a sample  bottle  at  once  to  prevent  absorption  of 
moistui-e  or  oxidation. 

After  being  washed  ivith  wther  the  residue  dries  very  rapidly 
and  thus  danger  of  much  oxidation  is  lessened.  No  quantitative  re- 
sults may  be  expected  shoiving  percentages  of  residue  and  extract 


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39 


o\?ing  to  chemical  reaction,  depo si tion  of  seleaiuni  and  lossof  small 
amounts  of  residue  through  repeated  wadiiing  and  fdl  teri.ng.B ecause  of 
this  loss  no  check  runs  are  possible.  The  nature  of  the  extract  sol- 
ution is  such  as  to  allov7  of  no  separation  of  Ihe  extracted  c^al 
sub  stance,  and  this  also  rmders  qiianti  tative  woric  impossible.  No 
extraction  and  filteration  process  ^\lthout  the  use  of  benzene  to 
aid  in  filtering  ivill  succeed  as  the  filter  clogs  and  the  reagoit 
rapidly  hydrolyzes  from  e^osure  to  the  air.  Rapid  manipul  ation, 
exclusion  of  moisture,  and  keeping  the  reagoit  well  mixed  with 
benz^e  \^iile  in  contact  v/ith  the  residue  and  exposed  to  the  air 
are  the  essential  safeguards  for  effective  use  of  this  extrQ!Tely 
simple  method  of  extraction. 

2’,  Examination  of  Products  and  Malysis: 

Very  little  attention  was  given  to  examination  of  the  extract 
solution.  Preliminary  tests  Crowed  that  any  separation  of  the  ex- 
tract material  from  the  coal  was  impossible  because  of  the  chemical- 
ly changed- nature  of  the  material.  The  extra  ct,p  rob  ably  resinic  in 
n atu re,  en ters  into  combination  with  the  reagent  and  is  thus  ciianged. 
Selenium  is  present  in  fairly  large  amounts  in  tiiis  extract  mass. 
Removal  of  this  selenium  may  be  effected  only  be  solvents  or  rea-en 
gents  vhich  at  the  same  time  ftirther  decompose  Ihe  extract. 

The  ether  washings  of  the  residue  were  mixed  tbgiether  and 
distilled.  Most  of  the  ether  was  recovered  pure,leaving  a small 
amount  of  heavy, black  extract  material,  b^ind.  This  was  added  to  th( 
extract  solution.  The  extract  solution  proper  contained  the  extract, 
selenium  oxychloride,  and  benzene.  ELI  trati  on, hydroly  si  s,  fractional 
distillation  and  other  methods  failed  to  isolate  the  extracted  sub- 
stance. Most  of  the  benzene  was  recovered  3Pa±rly  pure.  The  selenium 


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40. 

o clilo ri de  present  is  decomposed  to  give  primarily  selenious  acid 
and  red  selenium.  The  selenium  can  he  ronoved  in  part  hy  repeated 
hydrolysis  and  filtering.  Heating  the  solution  or  mixture  converted 
a portion  of  the  red  sel  oiium  to  the  gray  varlety,insoluhl  e in  any- 
thing hut  concentrated  sulfliric  acid,  \^ich  further  complicated  the 
investigation.lt  is  certain  that  there  is  some  form  of  extracted, 
coal  substance  present.  The  thi cfe, gummy , nature  of  the  extract  mass, 
left  after  the  henzene  and  selenium  oxychloride  have  heen  removed, 
shows  this  fact.  The  color  of  the  mass  is  hrov«i-hl ach,hu t the  pres- 
ence of  selenium  gives  the  mass  its  color  and  so  prevents  the  d.et- 
ermination  of  the  color  of  the  extract.  The  odor  of  the  extract  is 
that  of  rotten  radishes  vhich  diaracteri zes  selenium  compounds.  It 
tends  to  decompose  r?ith  evolution  of  heavy, hro^m  fumes  Then  heated 
in  the  air.  Distillation  only  dries  the  mixture  forming  a hard 
crust  like  dry  clay.  The  appearance  of  this  mixture  is  idoitical 
^vith  that  obtained  from  the  extraction  of  coal  with  the  xylene  dil- 
ution sol ven  t.  Th ere  is  one  difference.  In  the  former^  extraction 
there  was  present  a 3yl ene-sel enium  oxychloride  addition  substance, 
but  in  the  later  case  the  reagent  does  not  seon  to  react  vd  th  the 
benzene  in  the  least. 

The  residue  obtained  however  was  in  nearly  pure  form  and  from 
analysis  of  it  and  comparison  6f  the  analysis  with  that  of  the  or- 
iginal coal  it  v;as  thought  possible  to  determine  something  of  the 
nature  of  the  exti'act  as  well  as  of  the  residual  material.  To  free 
the  residue  as  prepared  from  selenium  it  was  desired,  to  extract  the 
residue  with  large  cju  an  titles  of  carbon  disulphide  in  which  the  red*, 
variety  of  selenium  is  soluble.  It  did  not  seem  probable  that  this 
extraction  wj[. th  carbon  disulphide  would  reailt  in  the  extraction  of 


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41 


any  of  the  coal  syb stance  from  the  resicJue  along  vdth  the  selenium,, 
hut  the  following  test  was  made  to  varj. fy  the  assumption. 

A small  amount  of  residue  from  a preliminary  extraction  with 
selenium  oxydiloride  ivas  analyzed  fo  r moi  stu  re,  aSh,  vol  atil  e m.atter, 
fixed  carbon,  total  carbon  and  sulfbr  content. No  coke  buttons  v.^ere 
left  from  tlie  volatile  determination,  and  the  presence  of  selenium 
and  chlorine  in  the  volatile  matter  was  shown  by  the  brilliant 
sparks  and  the  copper  ^vire  test  for  halogens.  Five  grams  of  the  same 
sample  of  residue  were  then  extracted  in  a so3hlet  apparatus  for 
twelve  hours  with  carbon  disulphide  to  remove  the  selenium  present. 
At  the  end  of  twelve  hours  the  residue  was  washed  free  of  carbon 
disLilphid.e  \vith  ether  and  dried  at  10 5 ’u.  Addition  of  ether  to  the 
CS2  and  cooling  Ihrew  the  seleaiium  out  of  solution.  Uiis  was  filter- 
ed off  and  weighed.  From  the  five  grams  of  residue  0.1198  grm.of  red 
selenium,  or  2.  39^,  were  obtained.  This  test  pointed  out  the  practi- 
ccbility  of  extracting  all  the  residue  with  carbon  disulphide  to 
obtain  a purer  residue  for  exanination.  The  an  all  selenium  free 
Sample  of  residue  v^ras  analyzed  for  moi  sture,  asai,  vol  atil  e matter  and 
fixed,  carbon.  The  results  of  these  analyses  tog  ether’  with  that  of 
the  original  coal  and  the  differences  are  shown  in  Table  V,  This 
table  shows, on  the  dry  and  pure  coal  bases,  that  the  only  effect  of 
the  US2  on  the  residue  is  a lowering  of  the  volatile  matter  by  8.670 
through  extraction  of  selenium  which  appears  in  the  analysis  as 
volatile  matter  largely.  The  fixed  carbon  is  correspondingly  in- 
creased by  3,6fc^  No  other  changes  in  tfie  analysis  of  importance, 
together  with  the  fact  that  evaporation  of  the  ether  and  carbon 
diailphide  used  failed  to  show  any  extract  material,  pixrved  that 
extraction  of  the  main  residue  ^vith  carbon  disulphide  does  not  re- 


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suit  in  any  loss  of  coal  material.  AccorcTingly  liie  main  residue  v/as 
extracted  in  a lar^e  soshlet  apparatus  xvi  tt!  two  portions  of  carbon 
disulphide  for  tliree  hours  vjhich  rejnoved  the  largest  part  of  the 
selQiium  present.  After  washing  with  ether  for  an  hour  the  residue 
was  dried  as  before  and  sealed  up  for  further  examination. 

Table  V. 

Air  diy:  Moisture  Volatile  A^  Fixed  C*  Total  C.  I^lflir 


Coal 

3.  33 

• 

CO 

9.02 

53.  39 

7 2.  17 

1.02 

Residu  e 

1.67 

50.78 

9.25 

38. 30 

51.04 

2.78 

Resi(iie“Se 

4.42 

46. 21 

9 . 06 

40. 21 

- 

- 

Difference 

1-2 

-1.66 

-(-16. 52 

+ 0.23 

-15.09 

-21.  13 

1.76 

Differoice 

1-3 

1.09 

+ 11.95 

+ 0.04 

' 13.  18 

mm 

Dry  basis: 


Coal 

- 

35.  42 

9.  33 

55.  25 

74.6  2 

1.05 

Residue 

- 

51.  50 

9. 39 

39.02 

51.86 

2.8  2 

Residu  e-Se 

- 

48.06 

9.42 

42.  52 

- 

- 

Difference  1-2 

- 

+ 16. 17 

+ 0.06 

- 16 . 23 

- 22.76 

4 1.77 

Difference  1-3 

- 

+ 12.64 

4-0.09 

-12.73 

- 

- 

Pure  coal  basis: 

Coal 

- 

39.08 

- 

60.9  2 

80.40 

- 

Residue 

- 

57.00 

- 

43.00 

57.  30 

3. 12 

Residu  e-Se 

- 

53.40 

- 

46.60 

- 

- 

Difference  1-2 

- 

t-  17.9  2 

- 

-17.9  2 

-23.  ID 

- 

Difference  1-3 

mm 

-f-  14.  32 

* 

- 14.  32 

mm 

43 


Ihe  main  residue  was  analyzed  on  iiie  Air  dry  l^asis.  The  com- 
plete analysis  is  s^ioAvn  in  Table  VI, 

Table  VI. 


Analysis  for; 

Air  Dry; 

Dry; 

Corabu  stibl 

Moisture 

2. 17 

- 

- 

Volatile  matter 

6 3.90 

6 5.  31 

70.90 

Ash 

7.76 

7.94 

mm 

Bixed  carbon 

26. 17 

26.7  5 

29. 10 

Total  Carbon 

54.89 

56.09 

60.93 

Sulfhr 

0.81 

0.84 

0.91 

Ni  trogen 

1.  50 

1.  54 

1.67 

Ojygen 

27.73 

28.34 

30.79 

Hy  drog  en 

5. 14 

5.  25 

5.70 

B.T.U. 

9,06 2.  2 

9,  261.  36 

Uni  t co  al 

10,  136.4 

4*  The  Effect  of  Selenium  o:^ciilo ride  Upon  the  Primary  Volatile 
Products  of  the  (Jarboni zation  of  Coal. 

1*.  Outline  of  Investigation; 

WiQi  coal  is  heated  in  the  absence  of  air,  such  as  ckiring  a cok- 
ing run , ch emi cal  reactions  occur  of  a compl ex  nature  and  new  sub- 
stances are  formed  in  place  of  the  oiTiginal  coal.  These  new  aib st- 
ances are;  the  solid  residue  or  coke;  liquid  products  in  the  form 
of  water  and  tar;  and  gas.  Hie  yield  and  character  of  tliese  products 
will  dep Old  upon  the  type  of  coal  used,  the  toiiperature  of  the  car- 
bon! zation,  th  e time  and  the  pressure.  Ihe  first  or  primary  volatile 
products  coming  off  are  ciiangecl  by  secondary  decomposition  if  allow- 
ed to  ronain  exposed  to  a sufficiently  high  temperature,  so  in  the 


44. 

average  high  t€»iperature  caiiDoni zation  mn  it  is  douhtfUl  \ihetfier 
any  of  the  final  products  are  liberated  from  the  coal  as  su(h.  Much 
information  as  to  th  e constitution  and  coking  properties  of  cx>al 
be  derived  from  a study  of  the  primary  proclucts  of  carboni  zation.  For 
this  end  it  is  necessary  that  the  products  be  r<anoved  at  once,  and 
that  the  temperature  and  time  of  the  run  be  respectively  neither 
too  high  nor  too  long. 

With  these  points  in  mind  and  cvi  th  a vievir  to  learning  more 
^out  the  type  of  residual  and  extract  material  obtained  from  cx)al 
by  the  use  of  selenium  oxychloride,  and  from  this  data  to  develop 
further  if  possible  the  ideas  of  carbonization  and.  the  constitution 
of  coal,  the  following  series  of  tests  were  made.  A study  of  fresh 
coal  was  first  made  by  means  of  low  tejiiperature  carbonization  runs. 
The  primary  volatile  matter  of  the  coal  was  liberated  leaving  an 
altered  cosCL  substance  or  residue  in  the  form  of  a partly  coked 
solid.  Parti culiar  attention  was  given  to  the  residue,  tar  and  gas 
products.  More  fresh  coal  was  then  treated  with  selenium  oxychloride 
to  r^ove  the  tar  forming  material  as  has  been  sho^vn,  and-  tliis  ex- 
traction residue  subjected  to  tlie  same  coking  process.  The  abs^ce 
of  tar  and  the  composition  of  residue  and  gas  were  noted  especnLally, 
and  compared  with  results  obtained  from  the  fresh  coal. 

The  results  of  this  part  of  the  investigation  were  intended  to 
varify  the  preceeding  work  and  to  add  to  this  investigation  infor- 
mation relative  to  tlie  amount  and  character  of  the  primary  volatile 
products  and  of  tiie  coke  residue  from  the  carbonization  at  low  ton- 
perature,  and  the  effect  of  seloiium  oxychloride  in  modifying  all 
these  factors. 


Since  one  of  the  main  products,  the  tar, is  removed  by  .the 
reagQit,the  composition  of  the  gas  given  off  up  to  the  point  where 


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45, 


the  tar  begins  to  distill  and  that  given  off  after  the  tar  is  all 
distilled  over  was  noted  especially.  For  this  reason  the  temperatur 
of  the  different  carbonization  runs  were  governed  by  the  tonperatur 
es  at  vihich  the  tar  first  showed  and  that  at  Thich  it  ceased  to 
distil.  Through  the  courtesy  of  Wade  S.Hawthome  the  temperatures 
of  theb^inning  and  maximum  softening  points  of  the  fresh  coal 
were  obtained.  Ihe  Franklin  county  coal  used  Ihroughout  this  inves- 
tigation begins  to  soften  at  37 4^0.  and  readies  its  maximum  soft- 
ened state  at  406  From  this  data  it  is  safe  to  assume  that  the 
tar  b^ins  to  distill  from  the  coal  around  37  5 *0. 

2*.  j^paratus: 

The  complete  carbonization  apparatus  is  ^owi  in  Figure  II. 

The  electric  resistance  fhmace  (A)  was  the  same  as  described  in 
Figure  I.  Exact  temperature  r^ulation  was  secured  by  means  of  the 
resistance  (B  ).  The  coking  retort  (u)  was  made  of  pyrex  glass  tubing 
50  mm. in  diameter  and  30  cm.  long.  A lOmm.  tube  or  side  arm  (O)  was 
sealed  on  about  10  cm.  from  the  top  of  the  retort.  The  retort  was 
held  in  the  furnace  in  a vertical  position  with  Ihe  upper  10  to  15 
centimaters  exposed.  Asbestos  paper  was  wrapped  around  the  exposed 
portion  to  aid  in  distilling  over  the  tar.  The  top  of  the  retort 
was  closed  with  a #8  one  hole  rubber  stopper  carrying  a pyrex 
til ermo coup  1 e tube  (E).  The  stopper  was  protected  from  heat  by  three 
aluminum  discs  (F)  placed  on  the  thermocouple  tube.  The  retort  act- 
ed as  a distilling  flask  with  the  side  arm  long  enough  to  act  as  a 
condenser.  The  end  of  the  side  arm  extended  well  into  a 50  cc.  dis- 
tilling flask  (G  ) in  which  tlie  water  and  tar  w^ere  collected.  The 
evolved  gas  passed  out  through  the  side  arm  of  the  small  distilling 
flask  into  a aaall  bulb  (H  ) filled  with  glass  wool, used  to  remove 


^i  rv.  - .''*.  * . ■»■>.■•  —V  .<t>;iAr^jL..^t^ 


i .•  J.tw^  fx 

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46 


the  tar  fog.  Ihe  U tubes  (I  and  J ) held  dilute  sulphuric  acid  for 
tlie  removal  of  ammonia  from  Ihe  gas.  During  runs  on  the  residue  from 
the  selenium  o^g?^ chloride  extraction  tJjese  tubes  also  removed  traces 
of  selQiium  from  the  gas.  One  of  these  U tubes  was  filled  with  lead 
acetate, vti desired,  to  remove  hydrogoi  sulphide  and  hydrogen  selo» 
ide.  From  this  purification  train  the  gas  passed  directly  into  a 12 
liter  aspirator  bottle  (L  ) \ihich  served  as  a gas  holder.  This  bottle 
was  graduated  into  25  cc.  divisions  and  the  gas  volume  was  measured 
here  as  well. 

3'.  Temperature  Oontrol  and  Measurement: 

The  fUmace  and  resistance  block  have  been  previously  mentioned 
Some  runs  were  made  ivithout  resistance  thus  allowing  the  coking  pro- 
cess to  proceed  as  rapidly  as  possible.  Others  were  conducted  more 
slowly.  The  time  and  temperatures  used  are  given  in  Ihe  tables  of 
data.  In  general  the  tonperature  was  not  carried  past  8 25*0  so  as  to 
guard  against  any  secondary  decomposition  of  the  pro du cts.  Tempera- 
ture readings  of  the  flimace  and  retort  were  talcen  approximately 
every  fifteen  minutes.  For  tonperature  readings  two  Ch rom el -Alum el 
th enno coupl es  (E  ) made  of  number  16  wire  were  used.  These  were 
connected  as  shorn  in  Figure  II.  to  a Weston  Direct  Current  Milli- 
voltmeter  (M ).  They  were  standardized  against  the  freezing  points  of 
Bureau  of  Standards  Aluminum  and  Tin.  The  couples  were  exact  dupli- 
cates and  the  same  tonperature  curve  was  used  for  both. The  tonpera- 
ture  could  be  read  from  the  curve  to  within  two  d^rees  and  the 
couples  were  accurate  to  the  same  extent. 

4*.  Proceedure: 

Thirty  grams  of  fresh  coal, or  residue  under  observation,  air 


E 


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A - Electric  Resistance  Etimace 
B - Resistance  Board 
C - Pyrex  Glass  Retort 
D “ Side-ann  Oondaiser 
E - Pyrex  Glass  Ih emo coupl e Hibe 
F - Aluminum  Uiscs 
G - Tar  Trap 
H - Glass  Wool 
I - U Thbe  ( 10^H2S04  ) 

J - U TUbe  ( Pb  acetate) 

K - Thenno couples 
L - A^irator  Bo  ttl  e l?l# 

M - Mllli voltmeter 


Eigure  II* 


48 


dried  and  ground  to  60  mesh  were  poured  into  the  retort.  The  ther- 
mocouple tube  and  stopper  were  inserted  so  that  the  lower  end  of  the 
thermocouple  tube  extended  down  th ree-fou rth s of  the  way  into  the 
coal  ciiai^e.  All  connections  were  made  as  shown,  and  the  apparatus 
exausted  of  air.  The  aspirator  bottles  were  used  to  exaust  the  air. 
During  the  carbonization  mn  a suction  was  maintained  upon  the  re- 
tort by  holding  the  leveling  aspirator  bottle  ftill  length  below  the 
gas  holder.  No  fhrther  attonpt  to  control  the  pressure  in  the  re- 
tort was  made.  The  suction  was  sufficient  to  take  off  all  volatile 
products  as  rapidly  as  formed  and  thus  no  secondary  heating  of  pro- 
ducts resulted-. 


5'.  Determination  of  Products  and  AnalyMs: 

As  has  been  stated  in  the  outline  the  most  important  products 
from  these  carbonization  tests  were  the  residues,  the  tar  aid  ihe  gas 
The  amount  of  residue  was  determined  by  weighing.  After  weighing  the 
coke,or  semi-coke  as  the  case  might  be, was  sealed  in  a small  sample 
bottle.  Ihe  water  and  tar  collected  together  in  the  tar  trap  were 
ranoved  and  centra fUged.  Very  few  attonpts  were  made  to  determine 
the  weight  of  the  water.  The  water  was  separated  from  the  tar  by  use 
of  a small  pipette  said  the  tar  weighed.  No  attonpt  was  made  to  det- 
ermine the  ammonia.  Ihe  gas  evolved  vfas  collected,  and  measured  in 
the  gas  holder.  Portions  representative  of  the  whole  were  removed 
from  the  holder  and  analyzed  in  a Modified  Orsat  Apparatus  (29), 
designed  and  built  in  this  l^oratory.  The  constituents  were  deter- 
mined as  follows:  OO2  hy  absoiTition  in  KOH,  O2  in  alkaline  pyrogallo 
^314  in  bromine  water,  and  C^Hg  in  filming  sulfliric  add.  H2  and  CX) 
were  burned  in  a copper  oxide  flimace  at  300  *C.,  the  H2  determined 
by  contraction  and  tiie  U)  by  absorption  of  the  resulting  00 2 


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49 


in  KOH#  CH4  and  C^Iq  were  burned  in  an  atmosphere  of  oxygen  over 
mercury  in  a glass  bulb  and  tlie  two  gases  calailatedby  Eamsiiaw’s 
(30)  method*  N2  was  taken  as  the  difference  between  the  total  of  the 
above  moitioned  constituaits  and  the  original  volume  ^ihich  was 
always  taken  as  exactly  100  cc.  thus  giving  the  values  obtained  in 
percQitage  by  volume* 

No  attonpt  was  made  to  analyze  tjie  tar*  In  tests  during  ^■hich 
hyd.rogen  sulphide  was  not  removed  from  the  gas  with  lead  acetate  it 
was  determined  as  (JO2  in  the  gas  analysis.  The  percentages  of  H2S 
are  so  anall  however  as  not  to  materially  effect  the  C0  2« 

Ye*  Results,  Part  II* 

1*  The  Effect  of  the  Tar  and  Volatile  Cont^t  of  Coal  Upon  the 
- Resulting  Action  of  Selenium  oxychloride: 

The  loss  of  resinic  extractable  matter,  that  is  tar  and  those 
hydrocarbons  forming  the  volatile  constituent  of  coal,  results  in 
lessening  very  greatly  the  action  of  selenium  o^ chloride  upon  coal. 
TJie  reagent  attaches  coal  in  proportion  to  the  amount  of  volatile 
matter  present  in  the  coal.  Coke  nhich  has  lost  its  volatile  matter 
and  tar  is  not  effected.  Partially  coked  coal  retaining  a portion  ol 
its  tar  is  attacked  giving  a gummy  extract  difficult  to  filter, 
nhile  with  freiSi  coal  the  selenium  oigr chloride  attacks  the  resinic 
material  and  un  saturated  hyd.ro  carbons*  Tar  is  not  thought  of  as  ex- 
isting in  coal  as  tar.  The  reagent  removes  those  hydro  carbon  s, mo  re 
especially  the  un  saturated  hydrocarbons,  and  those  resins  ^hich 
coked  or  distilled  yield  the  tar*  The  resinous  extract  taken  out  by 
the  reagoit  is  not  a pure  resinic  material, but  a new  compound  form- 
ed by  chemical  action  of  the  reagent  upon  tlie  resinic  material.  This 
results  in  the  gummy  sub  stance,  vhi  ch  being  mixed,  with  selenium  from 


'<  . s 


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50 


the  decomposed  reageji t,mal£es  filtering  impossible.  Water  will  not 
effect  this  extract, but  alcohol  will  aid  in  the  filtering  of  it. 

The  loss  of  the  coking  property  of  the  coal  at  the  same  time 
as  the  loss  of  the  tar  material  leads  to  the  conclusion  that  the 
bonding  material  of  the  coal  gives  the  tar  or  else,if  the  two  are 
separate  and  distinct,  th^  both  are  attacked  by  the  reagent.  A sol- 
ven;t  to  destroy  tlie  coking  properties  of  a coal  does  not  necessar- 
ily remove  the  tar  also.  Many  common  solvents  being  used  in  research 
at  the  presQit  time  Avill  destroy  the  coking  property  of  coal, but 
vihen  the  coal  residue  is  coked  it  continues  to  yield  tar,  though  pro- 
b^ly  not  in  such  large  quantities.  Seloiium  oxychloidde  is  unique 
in  this  respect  that  it  is  able  to  ranove,in  the  small  amounts  of 
coal  used,  all  traces  of  tar  from  the  coal  \hen  distilled. 

If  the  extracted  resins  or  tar  material  was  not  changed  chon- 
ically  by  the  reagent  it  should  be  possible  to  separate  it  by  hy- 
drolysis of  the  reagent.  Since  adding  vjater  does  not  effect  a sep- 
aration but  only  the  d.ecompo si  tion  of  some  remaining  selenium  oxy- 
chloride, it  is  safe  to  assume  that  chonical  action  fonning  some 
additive  compound  has  taken  place.  Ihe  residuesshould  be  cellulose- 
ic  material  if  the  data  we  have  is  correct  which  assumes  that  sel- 
^ium  o:^chloride  \idll  not  attack  cellulose.  Just  what  the  nature 
of  the  residue  is  ^vill  have  to  be  determined  by  analysis  and  by  the 
study  of  the  gases  formed  by  carbonization  mns  on  the  residue. 

The  Effect  of  Selenium  oxychloride  Upon  Coal; 

Selaiium  oxychloride  extracts  all  the  resinic  cinstituent  of 
coal  leaving  nothing  which  may  be  further  extracted  with  the  ordinal 
organic  solvents.  The  action  is  not  a solvent  one  but  chemical  in 
nature.  Powdered  coal  is  attacked  ^vith  the  evolution  of  heat. 


.t  -A  ^ 

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' ' f 


f “■■KCt  •''KlXi'-JOil'*'*'  ”,.'*■  'iv>  -'r'  ' ( '•'"•' 

f.*;;  * •'•  • •'  b -/I  . > 

^.»cT  .«!*'  '.K f-:, 

■'.'^X'Mf  ir' .'f  r:...-.  i r'?>  ; .-Jfr  «.>f»  «i  • '-'V  ':  . •..?*  '■  > fj(i, 

y .V  • ; , <'N.‘  ;j  ( Ao.n^"  > oit  r " ■' ' ‘fiif  .y^  rii» o '5.;!^  .■• 

• 'f 

’*,' ' ' ' ■ , / '' 

■«  ijpl  . 'JJr-  Mr  ■» " ' ^ ftbf  ' *'V  'i  a ’t 

:■  . •[  ^ i^' .j  ■•.  ■'/'ij/1  ck*'’'m:  ( V' tr;i <..*1  at>< 


*5  0 


V ,:  a 

r 


V.  '•  ’ 

r;.‘  ' 


: ' y <r<,i((P’U  iiji*  t*'  I .<  «(/-'■>  ' ,r*c.' 

Tj[>  ttf  ; J>;  r^'■^  *.»  y -J  f Jjj,  '.;,  > 'Vli.t'.. ; ' /i  !-t titoNK<ijif 

■ ’ * ! “ 

•.'  '..••■«  *■  - ' '-..-.iVi''  i.V.  '■/••  il*  ■"  ' ''■•  ^ 

' - v ' ■ •„•  : I-J.tiui  '•  ■'  V - 


.:.V  ‘ 

■? 


j r* 


4* 


51 


The  resinic  and  tar  fonning  constituent  of  the  coal  is  extracted 
leaving  the  cellulosic  and  mineral  part  of  the  coal. The  reagent 
reacts  at  once  \?ith  the  extracted  portion  to  form  new  complex  com- 
pounds. A portion  of  the  reagent  is  decorapo sed  hy  the  chemical  ac- 
tion resulting  in  the  deposition  of  red,  amoirphou  s selenium  through- 
out the  extracted  material. 

No  (pantitative  extraction  is  po ssihl e,  esp ed ally  from  the 
standpoint  of  the  extract.  There  is  an  extract  and  a residual  mat- 
erial,hut  the  extract  can  not  he  isolated  pure  and  separation  of  the 
reagent  from  the  residue  entails  losses  \ihi  di  prevent  quantitative 
wort.  BenZiOie  or  some  similar  inactive  substance  must  he  used  to 
protect  the  reagent  from  the  air  and  to  aid  in  filtering.  The  resi- 
due obtained  hy  filtering  may  he  made  fairly  pure  hy  extraction  with 
carbon  disulphide  and  washing  with  ether.  A small  amount  of  selen- 
ium and  chlorine  are  left  ini  the  residue  due  to  decomposition  of 
the  reagQit  \ihile  in  contact  with  the  residue.  A comparison  of  the 
original  <x)al  and  the  residue  upon  the  Dry  basis  is  shown  in  Table 
VII. 

Table  Vll. 


-Analysis  for: 

Coal . 

Residue. 

Difference. 

Volatile  matter 

35.42 

6 5.  31 

-f-  29.89 

A^ 

9 . 33 

7.94 

- 1.39 

Fixed  Carbon 

55.  25 

26.7  5 

- 28. 50 

Total  Carbon 

74.62 

56.09 

~ 18 . 53 

SulfUr 

1.0  5 

0.84 

- 0.21 

Nitrogen 

1.  55 

1.  54 

- 0.01 

Oxygen 

8.55 

28. 34 

+ 19.79 

Hydix>gen 

B.T.U. 

4.90 
13,  280 

5.  25 
9,  261 

^ 0.35 
- 4,019 

I.'  f 1 


b.’  ' .‘  •'■>;.:•  •(/; 


■ ':i,'  ;i?' 

, ,.  ‘ '■  i ' • ■ 0 ' >'J 

: ' ft.  a.-:  > |$|  }r, : rf;  i »> 

- 

y>)  ' 

J.f'Ol  1 IVO  JflJ  , '’ 

' ’■ 

.VX ' <» 

>•<!  , 'U  .*;  ^ • 

■>  ■ • ':  t rfi'  * - ■*•  J 

V :• 

i r ' (■•  j .)  V , , 4 ■ ■ ' 

- . -J  *' 

;:;  ./)0"  *!  '•:  ■ 

' i ' 

'•  ' 1 • 

.'■  i ■'©•f 

4. 

' K ■ 

■•;  in  ’ ' ■>.'  V *’•  .’ 

' 

::^i.'  V ..M  '•■iJ.:. 

idro  -o i 1 ' <i'  ■ f ' 't' 

ye'.. 

• •:  •: 

' ■ ■ 1 ,1  t ■ r 1 T 

■ : •.  '>  ' ' ,‘I>0  ; i:; 

1 

>■  .' 

f -0  • •«  t , ’ •'•  i'» 

^ • V 

•,:■  :■ 

fir  1 o . '.’  • f * ■■■  ♦ * 

■ ” i - 

' 'T  ^ 

..1?  .■»*,  X. 1' ; T i..''.’ 

r.'i^v  *r 0 i>l fi  . 

ij  - < •>' 


v-W 


M 0 

i ■ 

n Xif*^'’. 


'['I  J’vy  f 


iL  I.  ■’ 


■j/;  ('/r 

•)i#,  r Cfi  « ;.‘  • 


■ i t)  s 'L':.Id'*  0I»' 


' ■*  •>  "( 

';.*'  y .'  I 


V.  !;/  •.'.t-'-v  ' . ’ j ijT'  -ft  noift'' ‘ 

^ - IT  1 I !:f'tJ^  ■ ill; r ‘ ■ '.ai ^ 

• >Ai  ij  ■ -I.  Miijii  r 

d'  h ■•',■  4ij  • ^ 


( . 


li  ft^n-?-  '- 

iS’ii' 


'■  i 1/ 


) fS/nA 


UJjLilO 


r.  ^ 


. «•  >5 

. / >.  ; I 


r.<y  j • 

t ’ 

.4' 


f 


V-  .) 


52 


SelQiium  osy cJiloride  does  not  attack  the  nitrogen  of  the  coal. 
Practically  no  difference  was  found  in  the  nitrogen  content  of  the 
coal  andof  the  residue.  This  fact  is  varified  by  worij;  on  nitrogen 
of  coal  by  V.Bosbian  (31)  at  this  laboratory. 

Ash  shows  a slight  loss.  This  is  not  considered  important 
since  experimental  error  and  a very  little  extraction  of  some  ash 
constituent  such  as  pyidtes  will  account  for  this  loss. 

Sulfbr  ^ows  a very  slight  loss.  From  tliis  it  may  be  concluded 
that  the  residue  contains  practically  all  of  the  sulfhr.  This  is  to 
be  expected  since  the  ash  is  practically  unchanged.  A trace  of  org- 
anic sulfUr  may  have  been  extracted  or  extraction  of  a little  pyri- 
tes, Mhich  is  soluble  in  the  reagoi t,  woul d account  for  the  slight 
loss  in  both  the  ash  and  sulfUr. 

The  loss  in  carbon  contait  is  the  largest.  Probably  a little 
over  1/2  the  carbon  of  the  coal  is  present  in  the  residue.  The  car- 
bon of  the  extract,  that  is  the  resinic  constituoit  of  coal,  is  com- 
posed of  carbon  in  the  form  of  un saturated  hydrocarbons  and  bitumen. 

The  volatile  matter  shows  a lar^e  ^ain  due  to  loss  in  ash  and 
fixed  carbon.  The  organic  compounds,  ihi  (h  ^hen  heated  yield  volatile 
carbon,  are  not  attadced.  The  paraffins  are  included  among  tliese. 
There  is  a aaall  error  in  the  volatile  matter  due  to  tlie  burning  off 
of  traces  of  selenium  and  chemicals  such  as  benzene  vhich  make  the 
volatile  percent  too  high. 

The  heat  value  was  lowered  by  4,019  Btu.  or  31^  of  the  total 
heat  value  of  the  coal. 

Any  error  in  the  analysis  will  ^ow  in  the  hydrogen  and  oxygen. 
The  hydrogen  shows  a slight  inci*ease  in  the  residue  \4ii  ch  may  be 
due  to  experimental  error.  The  oxygen  content  of  the  residue  is  of 
special  interest.  A gain  of  nearly  18^  is  shown  \<hich  is  the  only 


i 


i 

J 

li 


*1 


i 


♦ 

i 

1 


1* 

1 


>.iv*4«» 


K, 


: < ^ 


U;  -•' 


*.^‘  t'/  ,.. 


•■sr 


pr(/,  ■ 'Vto.'l 

I*  ’ 


! ',' 


',  4 

. t L ; 

:s 


c ',  ‘t.'  • •'f.is  ■ 


Jv/. 


53 


sul)stantial  gain  in  any  single  constituent  of  itie  coal.  T^iis  leads 
to  the  conclusion  that  tiie  coal  ho  dies  extracted  were  very  low  in 
oxygen  and  that  there  was  a large  amount  of  oxidation  during  tire 
extraction  process,  lliis  oxidation  may  have  been  mechanical  oxida- 
tion or  more  probably  may  be  the  result  of  chemical  action  of  the 
reagent.  Oxidation  was  to  be  expected  ivith  sucii  a reagent  as  selen- 
ium o^  chloride. 

3.  The  Primary  Volatile  Products  of  Coal: 

Four  direct  carbonization  mns  were  made  first  on  the  fre^ 
coal.  These  runs  were  numbered  1,2,3  and  5.  Data  collected  on  tliese 
runs  and  analysis  of  the  gas  is  shown  in  Tables  V1II,IX, X,  and  XI. 

In  these  four  coking  mns  no  resistance  was  used  and  the  tempera- 
ture was  allowed  to  rise  until  the  point  set  for  the  conclusion  of 
the  mn  was  readied.  In  general  the  mn  was  terminated  iihen  the  tar 
had  all  beoi  distilled  over. 

Three  fractional  carbonization  mns  were  then  made,  mns  number 
6,7,  and  8.  In  these  mns  resistance  was  used  and  tiie  coal  <3iatge 
heated  up  slowly  in  order  to  get  the  maximum  yield  of  products  up  to 
any  certain  temperature.  In  Rm  6 and  7 two  cuts  were  made  in  the 
collection  of  gas.  The  first  fraction  or  cut  contained  tlie  gas 
evolved  up  to  tlie  point  at  vSiich  the  tar  begins  to  distil.  The 
second  fraction  consisted  of  the  gas  given  off  vhile  tlie  tar  was 
distilling,  aid  tiie  last  fraction  was  that  collected  after  all  the 
tar  had  been  removed  from  tlie  coal.  In  Run  8 one  more  fractional 
cut  was  made  to  differentiate  more  fUlly  between  the  gases  evolved 
after  the  tar  had  been  distilled  and  as  tiie  tetnperature  readied  the 
point  of  secondary  decomiio si tion.  Data  on  tliese  mns  aid  the  cor- 
responding gas  aialysis  is  sho^vn  in  Tables  XII, XIII,  and  }CIV. 


! - f'H,  , 


■>  )'/.•:'  '..  I,r.  tyi'  iV  '..0  •) . i 


■ ',;7  ua  • t^ 

itl  ,,i!^M!'  U <»•  0.<*i.;  ; ' -f  fcr«  ' 09^  ':• 

■H  ■ ' 7(/';’’  ' 

• J»o'  I..  » • 

r.'  \i ' 

(t^  ' 7 0 


’ rW. 


! » ;A  I 


X«1 
T,)  K' 


a,,  • '*!  ’*• 


■JVT 


,;  .'u 


, i 


.0  .M'i  ' . •^■‘ 


OJ* 


'.  f'V' 


.(.'  r 4 * \ I * I.  • ' 

’f  'f'o’V  ,'  '•-,  !-  'f  rf»<;  *m7  ^. ' ’ 0 

f M f/T;i  <>i>t 


>c;  ■ 


I..-  \.l- 


t* 

, i.F  -^11,1 . " ,;■  ^> 


I ■ '^• 


O' 


rv  tOt7fcja4..tJC  ' *' 


I ■ I - j 

*• 

f I «;0li 


t 

•;>o 


. '-Ca  •.4’^ 

> . ' ‘iliSk'ftd  >if.J  ; • ;/! 


:oo  ’O*-’ 


. ty>  ^ ijo  *t  0 ' 

. tf.»  OJ 

«iti  ■ .'  '■/■  • 

) .^  ' 0 i>  ^• 

1 1 ^ * ' • 

4 ’*>)("  ■■a'.: 

w •>‘^0  ■ ; 

i ? ♦ <"  f”  ' ■ 

• ' iJ5?j 

<rj  !•■■:.• 

i • ] 

*704''|U 

• ♦ 

.••  . *■ 

;'Oo  .yiT; 

r. 

.tv'IIJ-  '.v 

i/'  jvr  \^. 

' K.4 

h 

1,'*'  • 

0(0  . iij 

! f.f  / ' ' 1 

‘i  i^aiJaS  tlo.'; 
qqJ^?vr-'7 


Tatole  VIII 


54, 


DATA  ON 

DIRECT 

CARBONIZATION  RJN  #1. 

W eigh  t Co  al 

30  gnu. 

Air  did ed  Maki tan. 

Franklin  CO. 

Residue 

21.74  ” 

= 7 2.46% 

Tar 

1.  52  " 

= 5.00 

Type  of  residue: 

Good  coke  around  tli enno coupl e tube 

and  out  for  a- 

bout  half  the  diameter 

of  tlie  coke. 

Combined  Data  on 

run: 

Time  Temp  .Out  side  Tonp.  Center 

Gas  Volume  Ron  arks 

b 

p 

o 

Room 

Room 

0 

20 

190 

90 

190 

Moi  sture 

40 

340 

250 

390 

50 

375 

305 

425 

Much  waterover 

3;  00 

410 

400 

550 

Elrst  tar 

1 10 

430 

400 

750 

1 20 

455 

445 

10  50 

1 30 

470 

460 

1350 

1 40 

490 

480 

1660 

1 50 

505 

50  5 

207  5 

2 00 

510 

510 

2300 

Tar  still  coming 

2 10 

520 

530 

2500 

2 20 

520 

540 

27  50 

2 30 

525 

545 

2980 

2 40 

535 

555 

3200 

2 "50 

— 

565 

3370 

3 00 

560 

565 

3450 

3 10 

56  5 

580 

3700 

4 10 

&7  5 

610 

4400 

4 20 

575 

615 

4500 

Remaricst  A large  retort  was  used  and  qiiite  a little  tar  stucJc  to 
inner  wall  of  retort,  thus  giving  low  yield  in  trap. 


G as 

Data: 

Dupli cate 

! analy 

ses. 

I 

II 

Averag  e 

Temperature  maximum 

615* 

Time 

in  hours 

i 

4.  33 

Total  gas 

4500  cc. 

Gas 

analy  si  s- 

fo 

cc. 

% 

cc. 

% 

cc 

COp 

3.  5 

156 

6.0 

270 

4.8 

216 

® 2 

2.0 

90 

3.  5 

158 

2.7 

122 

^2P4 

2.6 

117 

2.4 

108 

2.  5 

IIS 

’-6^6 

.1 

5 

.4 

as 

. 3 

13 

H2 

30.0 

1350 

22.  2 

999 

23. 1 

117  5 

U) 

4.  5 

203 

6.4 

288 

5.  5 

247 

Ol4 

28. 1 

123  5 

30.6 

137  5 

29. 3 

1320 

7.6 

343 

7.6 

343 

7.0 

343 

N2 

21.6 

97  2 

21.9 

98  5 

21.  2 

9 51 

55, 


Table  IX, 

DATA  ON  DIRECT  CARBONIZATION  RUN  #2, 


V/ eight 


Coal 

ResLtoe 

Tar 


30.00 

20,8 

3.8 


gm. 

If 


Air  dry  Malcitan. 
= 69. 3^!^. 

= 12.6 


Type  of  residue: 

Same  type  of 

semi  coke. 

Combined  data  on 

mn: 

Time 

Toup.  Out  side  Temp.  Center  Gas  Volume  Remaiics 

0 ’00” 

148 

90 

0 

JNo te  retort  ho 

15 

265 

155 

200 

30 

330 

275 

260 

1 00 

340 

450 

1200 

1 15 

430 

455 

17  25 

Tar  still  dist 

1 30 

465 

525 

2500 

1 45 

525 

560 

3000 

2 00 

575 

3450 

If  II 

II 

2 15 

-i 

500 

3700 

2 30 

575 

620 

4000 

2 40 

— 

6 25 

4200 

3 30 

6 35 

4800 

II  II 

n 

4 30 

630 

650 

517  5 

Tar  all 

off 

6 50 

650 

660 

5700 

Gas  Data: 

Dupli cate 

analyses 

I 

II 

Average 

Tonperature  maximum  680 

1 

Time  in  hours 

6.8 

Total  gas 

5?00 

cc. 

Gas  analyst s- 

% 

cc. 

fo 

cc. 

fo 

cc«  N 

2 free 

3.0 

171 

2.  5 

142 

2.7 

154 

3.1 

o| 

2.0 

114 

2.1 

120 

2.1 

120 

2.  4 

2.0 

114 

1.8 

10  3 

1.9 

108 

2.  2 

• 5 

29 

.6 

34 

.6 

34 

.7 

H2 

34.  5 

1907 

33.2 

1890 

33.8 

19  28 

39.4 

U) 

7.7 

438 

7.1 

404 

7.4 

422 

8.6 

UI4 

29.7 

1690 

35.  3 

2015 

32.  5 

18  52 

37.8 

^2?6 

7.0 

399 

3.  2 

182 

5.1 

^1 

5.8 

N2 

13.6 

77  5 

14.  2 

808 

13.9 

79  3 

0.0 

Table  X. 


56 


DATA  ON  DIRECT  CARBONIZATION  RUN  # 3. 

W eigh  tCoal  30.00  gnn«  Air  dri  ed  M al:i  tan 

Residue  22.07  " = 7 3.55^ 

Tar  3.6  ” = 12.0 

Type  of  residue:  About  half  cjoked. 

Combined  data  on  nml 


Time  Temp.Ou tside  Temp*  Center  Gas  Volume  Ronarks. 


o 

o 

o 

3 

1 

Room 

Room 

0 

40 

300 

200 

250 

1 10 

415 

360 

400 

Mudi  water  off 

1 45 

425 

375 

450 

Tar  starting 

1 55 

450 

415 

680 

2 00 

485 

455 

1100 

2 15 

500 

480 

1500 

2 30 

525 

500 

1900 

Tar  still  coming 

2 45 

560 

540 

2500 

tVhite  fUmes 

3 05 

590 

56  5 

30  50 

Gas  data: 

Duplicate  an 

aly  ses 

I 

II 

Average 

Temperature  maximum 

565* 

Time  in  hours 

3.00 

Total  gas 

30  50  cc. 

ysi  s: 

N 2 free  i° 

cc. 

I0 

cc. 

I0 

CC. 

CO2 

4.  3 

3.0 

92 

3.  5 

107 

3.  3 

101 

°2 

5.6 

4.4 

134 

4.3 

131 

4.  3 

131 

C2P4 

3.9 

3.0 

92 

3.0 

92 

3.0 

92 

.8 

.7 

21 

.6 

18 

.6 

18 

h| 

2?. 4 

20.4 

6 22 

21.6 

660 

21.0 

641 

00 

7.7 

5.6 

171 

6.2 

189 

5.9 

180 

Ul4 

43. 1 

35.4 

108  2 

30.6 

9 35 

33.0 

1007 

7.2 

4.4 

134 

6.7 

204 

5.  5 

168 

N2 

0.0 

23.  1 

70  5 

23.  5 

717 

23.4 

713 

■ - ’ ^ ' 


V 


i 

f,y)f 


t 

< ■■ 

MM 


4L  ^ ,d 


37 


Table  XE. 

DATA  ON  DIRECT  CARBONIZATION  HJN  # 5, 

Weight  Coal  30,00  gm.  Air  dri ed  Maki tan. 

Residue  22,98  ’•  = 76,6^ 

Tar  1,69  " = 5,7 

Type  of  residue:  Excellent  coke.  Hard  and  'iihole  mass  coked. 
Combined  data  on  run: 


Time 

Temp.  Out  side 

Temp.  Center 

Gas  Volume 

Ronarlcs 

0 *00" 

Room 

Room 

0 

Occluded  gas  at  40 

15 

110 

55 

90 

30 

240 

155 

230 

Moisture  on  retort 

45 

310 

285 

300 

Water  over 

1 00 

355 

345 

425 

Tar  at  400  * 

1 20 

- 

445 

1000 

1 25 

500 

470 

1250 

1 40 

525 

505 

1800 

1 55 

- 

530 

2450 

Tar  off 

G as  an  aly  si  s data: 

IXipli  cate 

analyses 

I 

II 

Averag  e 

Tonperature  maximum 

530  ’ 

Time  in  hours 

2,0 

Total  gas 

2450  cc. 

Gas  analysis: 

cc,  % 

, 

0 

0 

N 2 fTee 

0O2 

2,6 

2.  3 

2.  5 

3.7 

®2 

6,4 

6.6 

6.  5 

9,7 

v/^4 

3.  5 

3.9 

3,7 

5.  5 

.7 

.7 

.7 

1.0 

H2 

12.  3 

11.  5 

11.9 

17,8 

xJO 

4.4 

5.4 

4.9 

7.3 

^4 

26.8 

30.4 

28.6 

43.0 

9.4 

6.7 

8.0 

12.0 

N2 

33,9 

32.  5 

33.  2 

0.0 

In  Figure  III, 

are  plotted 

the  curves 

for  these  coke 

! runs.  ' 

time  is  plotted  against  tonperature.  The  airves  in  black  ink  are 


for  tlie  four  direct  carbonization  mns,  and  those  in  green  for  the 
three  fractional  runs,  Figure  iV,  ^ows  tlie  time  plotted  against 
tJie  volume  of  gas  eveolved,  and  Figure  V,  the  tonperature  against 
the  volume  of  gas.  The  same  colors  are  used  throughout  to  indicate 
certain  coke  nms. 

Figures  VI,  to  XIV,  inclusive  show  graphs  of  the  individual 
constituents  of  the  gas  as  analyzed.  Percentage  composition  is 


I ' 


^ L 1. 

I 

ill.  L 

r,:r  l 


A tj'.rp', 


at  ■• 

..  » I 


■/ 


? 


\ \ I 


..•  ./\j- 


tn: 


> . < 


58 


plotted  against  the  temperature.  Eacii  an  all  circle  on  the  graphs 
indicates  the  percentage  composition  of  that  constituent  in  tlie  gas 
fraction  for  tiiat  temperature.  The  rise  or  fall  of  any  certain  con- 
stituent of  the  gas  during  any  given  tonperature  cut  or  fraction 
may  be  determined  by  reading  the  curve  betv/een  tlie  points  represent- 
ing the  two  cuts  in  question.  A glance  at  tJie  charts  will  show  that 
of  the  four  direct  carbonization  rans  Number  2 curves  vary  consid- 
erable from  Numbers  1,3,  and  5 vhich  all  lie  practically  together. 
Number  2 may  therefore  be  omitted  from  consideration  w!ien  drawing 
conclusions.  One  of  the  three  fractional  carbonization  curves,#3, 
also  shows  a divergmce  in  nearly  all  the  charts  from  the  other  two 
which  run  practically  together.  Numlsrers  7 and  8 may  therefore  be 
talcQi  as  standard  curves. 

A study  of  the  Tables  and  Figures  submitted  in  connection  with 
the  seven  direct  and  fractional  cxrking  runs  made  on  fre^  c»al 
shows  the  following  facts: 

Coke-  The  resiclies  varied  from  a semi-coke  to  well  coked  mass. 
Very  different  results  were  obtained  from  Taylor  and  Porter’s  (32) 
woric  in  vhich  they  state  that  ’’slow  carbonization  tarids  to  increase 
the  yield  of  coke”.  Table  XV,  giving  the  percentage  yields  of  coke 
and  tiie  time  of  the  run  for  the  direct  carbonization  runs  1,2,3  and 
5 shows  that  tire  yield  of  coke  for  these  runs  was  inversely  propor- 
tional to  tire  l^gth  of  the  run.  The  best  coke  came  from  the  runs 
of  shortest  length. 

T^le  XV. 

Run  Yield  of  coke  Time  in  hours 


2 69.3  6.8 

1 7 2. 46  4. 3 

3 7 3.5  3.0 

5 76.6  2.0 


The  average  yield  of  coke  for  tlie  seven  runs  was  7 2.1%. 


V • 


, T*  I A 


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50 


Tar-  Ihe  average  yield  of  tar  for  the  sevoi  runs  was  8,2fo,  In 
general  the  higher  the  tem]3erature  and  tiie  longer  the  period  of 
carbonization  t?ie  larger  was  tlie  jl'ield  of  tar.  The  first  sign  of 
tar  coming  over  varied  from  33 5 ’ -400  * U.  , wi tli  an  average  of  38  5*C. 
This  average  t^perature  of  the  first  appearance  of  tar  is  just  ten 
d^rees  higher  than  the  softening  point  of  the  coal  375* C.  The  tar 
v/as  all  off  from  50  5 *-6  50*0.  Uie  average  temperature  of  the  end 
point  of  tar  distillation  being  556  *0. 

Water-  Water  condensed  out  into  the  side  arm  of  the  retort  at 
from  100  *-230  *C.  Heavier  condensation  of  water  varied  from  28  5*  -36 E 
^vith  an  average  of  331*0. 

Time  and  Temperature-  Uiring  ttie  four  direct  carbonization 
runs  tlie  temperature  rose  rapidly  for  one  and  one-fourth  hours.  At 
this  time  the  temperature  averaged  around  390*0.  From  this  point  on 
the  temperature  rose  much  more  gradually  witli  the  leigtti  of  time. 

The  point  of  falling  off  of  temperature  rise  with  time  coincides 
with  the  start  of  the  tar  distillation. 

Temperature  and  Volume  of  Gas-  Figure  V.  ^ows  that  the  ex- 

ception of  Hun  6,  the  volume  of  gas  over  at  any  certain  temperature 
was  approximately  the  same  for  all  tlie  mns.  The  fractional  carbon- 
ization curves  ^ow  a larger  amount  of  gas  at  any  tonperature  than 
the  other  four  curves, naturally  because  the  time  was  longer  and 
resistance  bMng  in  tlie  coal  was  exposed  to  any  given  teirp eratu re 
for  a longer  time  allowing  more  decomposition.  However  the  differ- 
ence is  not  great.  The  curves  show  ttiat  up  to  about  375*  the  evolu- 
tion of  gas  is  gradual.  At  this  point  tiiere  is  a rapid  evolution  of 
gas  ¥hi ch  continues  to  about  450  * after  Miidi  the  curves  siiow  a 
steady  evolution  of  gas  with  no  sudden  changes.  The  distillation  of 


‘i  ' 


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water  of  decomposition  and  tar  is  coincident  with  the  rapid  diange 
in  the  rate  of  gas  given  off.  Table  XVI,  shows  the  relation  of  t^p- 
erature  and  time  to  the  volume  of  gas. 

Table  XVI, 


Rm  Time  in  hours  Maximum  Temp.  Volume  of  gas. 


5 

2.0 

530 

2450  cc 

3 

3.0 

565 

30  50 

1 

CO 

• 

615 

4500 

2 

6.8 

660 

oroo 

Oart)on  Dioxide-  Maly  sis  of  gas  fractions  shows  that  CO  2 is 
present  below  350*0,  It  increases  after  tlie  tar  starts  distilling 
and  up  to  about  525*  ^vhere  the  high  point  is  reached.  From  this 
point  on  and  in  that  portion  of  gas  collected  after  the  tar  is  all 
off  the  percentage  of  carbon  dioxide  rapidly  decreases.  Less  than 
2fo  remains  in  gas  at  6 25*0.  The  data  tallies  for  mns  1,2,3  and  5 
show  that  tlie  total  amount  of  carbon  dioxide  yielded  increased  in 
the  order  of  mns  5-3-1  and  thQi  fell  off  rapidly  in  mn  2,  Table 
XVr,  shows  that  5-3-1  is  the  order  of  mns  in  \^ich  time,  terapera- 
ture  and  gas  volume  increased.  Run  2 ^idi  took  tlie  longest  time 
and  reached  the  highest  maximum  temperature  Mows  the  snallest  amoun 
of  total  CO  2»  may  conclude  that  LO2  increases  ^vitti  tQnperature 
up  to  about  615*  as  shorn  in  tlie  graph,  and  then  rapidjy  falls  off 
as  tlie  tanperature  increases  and  secondary  decomposition  begins. 

O^grgQa-  Maly  sis  of  fractional  cuts  of  gas  shows  high  oxygen 
content  below  350*. As  the  tar  distills  tlie  percentage  of  oxygen 
rapidly  falls  off.  After  the  tar  is  off  the  o:^gen  remains  practi- 
cally the  same  until  600*  is  readied  after  itiich  it  falls.  The  totals 
Mow  til  at  oiygen  content  deoreased  in  tlie  order  of  mns  5-3-1-2  as 


) 


f- 


f 


1. 


C • 


61, 


the  taiiperatiire,  time  and  gas  volume  increased.  Oxygen  is  present 
in  highest  quantities  in  tlie  f^rst  gas  given  off*  by  carbonization 
of  coal.  Mud!  of  this  is  held  mechani cally  aiid  is  due  to  weatiiering. 

Unsaturated  Hydro  carbon  s-  are  very  low  in  gas  given  off  by 
coal  before  the  tar  starts  to  distill.  From  37  5’  tlie  percentage 
rapidly  increases  until  a temperature  of  apprxjximately  525’  is  reach 
ed.  From  tlien  on  until  6 25’  the  percentage  f all  s,practi  cally  no 
un satu rated  hydrx)  carbons  cxrming  off  above  6 25 ’C. 

Baizene  or  Saturated  Aromatics-  lire  curves  for  benzene  are 
nearly  identical  with  tliose  for  tire  unsatui^ated  paraffins.  There  is 
quite  a little  variation  in  the  benzene  curves  due  to  the  fact  that 
sudi  anall  amounts  are  present.  Benzene  is  formed  from  the  unsat- 
urated paraffins  upon  the  distillation  of  the  c»al  and  therefore 
its  content  in  gas  depends  upon  the  amount  of  etJiylene  present. 

Carbon  Monoxide-  Only  a small  amount  of  00  is  found  in  gas 
below  37  5 ’C.Incompl ete  oxidation  of  cellulose  upon  decomposition 
accounts  for  its  presence  at  this  stage.  From  ttie  point  of  distilla- 
tion of  tar  up  until  tlie  UO  3 begins  to  de<x)mpose  tlie  percentage  of 
00  slowly  increases.  From  600  ’ on  there  is  a rapid  rise. 

Etiiane-  is  practically  all  given  off  during  the  time  the  tar 
is  distilling.  Rise  and  fall  are  very  sudden. 

Methane-  goes  parallel  to  ethaiie.  Practically  all  is  given  off 
while  the  tar  distils. 

Hydrogen-  A small  amount  of  hydrogoi  is  given  off  before  t2ie 
tar  b^ins  to  distil  due  to  decomposition  of  cellulo  se.  From  5?5’  the 
rise  is  very  rapid.  Tli ere  are  two  points  of  sudden  rise.  First  about 
560’  vSien  the  resinic  material  starts  to  decompose  rapidly,  and 
second  after  650’  when  Secondary  decomposition  is  beginning. 


r ; * ' 


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TaJDl  e 

xri. 

DATA  ON 

FRACTIONAL 

GARB  ON  I Z ATE  ON  RUN  #6. 

Weight  ooal 

30.00  gnn 

. Fresh  M alii  tan. 

Residue  21,20  ” 

= 70. 

9fo 

Tar 

2.00  " 

= 6. 

7 

Type  of  residue:  Sesni  coke. 

Combined  data 

on  mn: 

Time 

Temperature 

Gas  Volume 

Remariis 

0 '00" 

Room 

0 

3.00 

First 

365 
cut  - 

1375 

First  tar 

0 00 

365 

0 

6 45 

Second 

525 
cut  - 

4550 

?.Iu  ch  water 

and  tar 

0 00 

525 

0 

2 25 

620 

1900 

Last  cut  - 

Gas  Data: 

Fractions  or 

CU  ts 

I 

II 

III 

To  tal 

Temperature 

365 

525 

620 

630 

lime  in  hours 

3.0 

6.7  5 

2.42 

12.  2 

To  tal  G as 

137  5 cc 

4550 

cc 

1900  cc 

78  25  cc 

Gas  analysis: 

% cc. 

fo 

cc. 

fo  cc. 

fo  cc* 

OOg 

0.0  0 

6.7 

305 

1.0 

19 

4.  1 

324 

® 2 

18.3  251 

4.8 

218 

5,8 

110 

7.4 

579 

0^4 

^6^6 

. 2 3 

1.7 

78 

. 2 

4 

1. 1 

85 

0.0  0 

. 5 

23 

. 2 

4 

.3 

27 

^2 

1.0  14 

22.8 

10  38 

55.0 

1045 

26.8 

2097 

U) 

1.9  26 

3.9 

314 

7.0 

133 

6.0 

47  3 

CH4 

0.1  1 

27. 3 

1242 

33.8 

518 

22,  5 

1761 

CsHfi 

0.0  0 

3.7 

168 

1.  3 

25 

2.  5 

193 

N2  78.5  1080 

25.6 

1164 

2.7 

42 

29.  3 

2286 

Ni  trogoi 

free- 

OOo 

0.0 

9.0 

1.0 

5.8 

0 2 8 5.  1 

6.5 

6.0 

10. 5 

cigHd 

.9 

2.  3 

.2 

1.6 

O0H6 

0.0 

.7 

.2 

.4 

H2 

4.7 

30.6 

56.5 

38.0 

00 

8.8 

9.3 

7.2 

8.5 

OH4 

.5 

36.8 

27.6 

31.7 

^^6 

0.0 

4.8 

1.  3 

3.5 

6 3 


Table  Xril. 

DATA  ON  FRACTIONAL  CARBONIZATION  RJN  # 7. 


Weight  Coal  30.00  gnn.  Fresh  Makitan 
Residue  21.0  5 '*  = 70.1% 

Tar  2.30  " = 7.3 

Type  of  residue:  Serai  coke.  Not  hard  but  extronely  fragile. 
Combined  data  on  run: 


Time 

Tonperature 

Gas 

Volume 

Ranaili  s 

0 ^00" 

boom 

0 

2 30 

395 

600 

First 

tar  over 

First 

cut  - 

0 00 

395 

0 

4 30 

56  5 

3000 

Second 

cut  - 

0 00 

570 

0 

1 50 

620 

1500 

Last  cut  - 

Gas 

data: 

Fractions  i 

or  Cuts 

I 

II 

III 

To  tal 

TonperatLire 

39  5' 

565’ 

630  ’ 

630  ’ 

Time 

in  hours 

2.  5 

4.  5 

1.8 

8.8 

To  tal  g as 

600 

3000 

1500 

5100 

G as 

analy  si  s: 

fo 

cc. 

fo 

cc. 

% 

cc. 

cc. 

OOp 

4.9 

29 

5.  1 

153 

1.8 

27 

4.1 

309 

02 

15.  2 

91 

.9 

27 

2.8 

42 

3.  2 

160 

0^4 

.6 

4 

2.9 

87 

.3 

4 

1.9 

95 

OgHg 

0.0 

0 

.7 

21 

.1 

1 

. 5 

22 

H2 

18.0 

108 

20.0 

600 

54.0 

810 

29.8 

1518 

00 

2.  3 

14 

8.4 

252 

8.5 

128 

7.7 

394 

CH4 

13.  5 

81 

2?. 8 

8 34 

27.0 

40  5 

25.8 

1390 

1.0 

6 

9.0 

270 

1.  2 

18 

5.7 

294 

N2 

44.  5 

367 

25.  2 

750 

4.3 

65 

21.  3 

1088 

Ni  trogen 

free 

002 

8.8 

6.8 

1.9 

5.  2 

0 2 

27. 5 

1.2 

2.9 

4.0 

0^4 

1.1 

3.9 

. 3 

2,4 

0.0 

.9 

.1 

.6 

H2 

32.4 

2r.o 

56.4 

37.8 

ijff 

4.  2 

11.4 

8.0 

9.8 

^4 

24.3 

37. 2 

28. 2 

32.8 

1.8 

11.6 

1.3 

7.4 

N2 

0.0 

0.0 

0.0 

0.0 

K 


/ .)  rr/* 


0 

mt' 

o 


r;u.r  - aJC^Si 

\ ,• ' ■ 


' i| 


34 


Tsifole  XIV, 

DATA  ON  FRACTTONAL  CARBONIZATION  RUN  #8. 

Weight  Coal  30.00  gnn.  Fresh  Makitan. 

Residue  21.7  2 •’  = 7 2.4^ 

Tar  2.40  ” = 8.0 

Water  3.30  ” = 11.0 

Type  of  residue:  Soni  coke.  Not  hard.  Poor  quality  due  to  length  of 

time  of  caihoni  zation. 

Gas  Data:  Fractions  or  Uits 


I 

II 

ill 

IV 

Total 

Temperature 

375’ 

50  5’ 

575’ 

620  ’ 

620  ’ 

Time  in  hours4.  2 

3.  25 

3.00 

0.  5 

11.0 

Total  gas 

800 

2500 

1370 

1100 

5770 

Gas  analysis: 

I0 

% 

% 

/<= 

I0 

U)2 

3.3 

7.3 

3.6 

0.0 

4.  5 

0 2 

16.4 

2.  5 

2.  2 

1.0 

4.1 

C^4 

0.0 

4.1 

0.5 

0.4 

2.0 

0.0 

1.0 

0.0 

0.0 

.4 

K2 

0.8 

19. 1 

27. 2 

54.6 

25.  2 

U) 

1.3 

3.  5 

10.4 

8.3 

5.7 

(JH4 

0.  3 

21.  2 

32.  2 

29. 5 

22.6 

0.0 

8.6 

0.0 

1.4 

4.0 

No 

77.9 

32.7 

23.9 

4.8 

31.  5 

Combined  data  on  mn: 

Time 

Temperature 

Gas  Volume 

Remarits 

0 ’00” 

Room 

0 

100 

Sign  of  moisture 

240 

Larger  distillation 

1 40 

265 

400 

\irater  of  decomposi 

1 50 

285 

400 

2 20 

305 

500 

2 45 

330 

540 

2 55 

340 

580 

Much  more  water 

4 10 

375 

800 

First  tar 

rst 

cut  - 

0 00 

375 

0 

20 

385 

200 

40 

395 

250 

1 00 

420 

500 

1 20 

435 

900 

Tar  still  coming 

1 40 

455 

1300 

3 05 

49  5 

2450 

3 15 

505 

2500 

Last  of  tar 

— 

Second  cut  - 

0 00 

510 

0 

2 30 

520 

1000 

3 05 

575 

1370 

Third 

cut  - 

0 00 

580 

0 

30 

620 

1100 

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7 3 


To  summarize  tiiis  data  it  may  be  stated  tiiat: 

1-  More  til  an  two -thirds  of  tlie  oi^anic  substance  of  coal  is  decom- 
posed at  temperatures  below  500 'C.  The  ronainder  in  mostly  decompos- 
ed betweai  500  ’-600 

2-  Coke  may  be  obtained  from  fresii  Illinois  coal  of  the  type  used 
in  this  investigation.  Fast  coking  of  the  charge  tends  to  increase 
the  yield  of  coke.  Heating  slowly  over  a long  length  of  time  tends 
to  destroy  the  coking  property. 

3-  Low  temperature  carbonization  yields  a higher  percentage  of  tar 
than  the  high  tonperature  process.  An  average  yield  of  8.2^  is 
obtained  by  the  method  here  used.  The  tar  b^ins  to  distil  at  385’ 
and  is  practically  all  off  by  560  ’C. 

4-  Ordinary  moisture  of  coal  is  driven  off  at  10  5 ’O.  Water  of  dec- 
omposition of  coal  is  produced  from  coal  in  largest  amounts  above 
250’.  This  water  of  decomposition  is  mostly  off  by  500’,  tire  larger 
distillation  coming  amund  330’.  ihe  largest  part  of  tire  water  of 
coal  thoi,  consisting  of  moisture  and  water  of  decomposition,  is 

ou  t by  500  ’• 

5-  Rise  of  temperature  in  coking  retort  proceeds  more  rapidly  during 
the  first  two  hours  of  carbonization  than  later  on. 

6-  Coal  brealcs  down  at  all  tonperatures  more  or  less.  At  tempera- 
ture of  normal  atmospheric  temperature  tfie  process  is  one  of  oxida- 
tion or  weatliering.  The  temperature  at  Miich  reactions  occur  to  any 
extent  in  experim^tal  time  must  be  considered  above  atmospherd.c 
tonperature.  Bituminous  coals  of  ttie  type  used  begin  to  decompose 
and  distil  between  150 ’-200 ’C. 

7-  The  first  decomposition  o ecu  ring  as  the  temperature  is  raised  is 
the  breaking  do\wi  of  ttie  cellulosic  substance  of  the  coal. The  first 


....  . . 


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7 4. 

primary  proclucts  of  decomposition  being  chiefly  water  of  decomposi- 
tion, iX)  and  OOg.  At  285*  Ihe  water  of  decompo  si  tion,  00,  CX3  2 and 
oxygQi  predominate. 

S-  At  approximately  331’  tiiere  is  a large  increase  in  the  yield  of 
gas  accompanied  by  a larger  amount  of  water  of  decomposition  and 
!9nall  percentages  of  hydrogen*  Organic  compounds  here  b^in  to  breaJc 
down  as  evidenced  by  presence  of  82^*  Liquid  and  gaseous  hydrocar- 
bons higher  than  methane  have  begun  to  distil  before  this. 

9-  At  38  5’  comes  a larger  distillation  of  paraffin  hydro  carbon  s.  Tar 
un saturated  hydro  carbon s, ben zQie,  ethane  and  methane  predominate. 

10-  At  450*  there  is  a second  heavy  evolution  of  gas.  Paraffin 
hydro  carbons,  CO  2>  and  water  of  decomposition  no^v  predominate.  The 
coal  is  still  producing  gases  \iiich  kill  tJie  coking  property  by 
preventing  tlie  bonding  togetlier  of  the  coal  material. 

11-  Between  525’-G00*  the  paraffins  mn  out  and  OO2  b^ins  to  dec- 
ompose increasing  the  yield  of  00  and  o:^gOi.  The  yield  of  un sat- 
urated hydrocarbons  has  readied  a maximum  and  the  hydrogen  is  in- 
creasing. 

12-  By  500*  two  tliirds  of  the  organic  substance  of  the  coal  is  de- 
composed. The  last  water  of  decomposition  is  coming  over  and  tjie 
distillation  of  tar  is  falling  off. 

13-  Between  625’-650*  formation  of  benzene  is  stopped.  Tiie  tar  is 
practically  all  off  and  mudi  more  hydrogen  is  in  evidence  in  the  gas  . 

14-  These  tests  were  not  carried  to  a higher  temperature.  Above  650' 
there  is  a final  distillation  of  volatile  matter  from  tlie  heavier 
hydro  carrions  and  resini  c materi  al  of  the  coal.  Secondary  decomposi- 
tion sets  in  around  700  *C. 


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Table  XVII. 

DATA  ON  fractional  CARBONIZATION  lUN  #9  ON  RESIDUE. 


Weight  charge  30.00  gm.  Residue  from  selenium  oxjr chloride  ext. 

residue  20.44  ” =68.1^ 

No  tar  and  only  a few  cc*  of  water  came  off. 

Dilute  sulfuric  add  and  lead  acetate  bo ttl es  in  train. 


Type  of  residue:  Fine  powder  in  appearance  like  original  chaise. 


Combined  data  on  mn: 


Time 

Temperature  Gas  Volume 

0 *00" 

Room 

0 

1 00 

210 

700 

1 20 

265 

1300 

1 45 

290 

1700 

2 00 

315 

1900 

2 15 

325 

2100 

2 35 

340 

2300 

2 45 

345 

2400 

3 05 

360 

2550 

3 30 

363 

27  50 

3 45 

375 

First  cut  “ 

2800 

0 00 

375 

0 

1 00 

450 

10  50 

2 25 

600 

Second  cut  - 

3100 

0 00 

600 

0 

10 

60  5 

300 

40 

60  5 

6 50 

55 

620 

Last  cut  - 

900 

Data: 

F’raction  s 

or  cuts 

Ron  ark:  s 

Much  moisture  vapor. 


Trace  of  Se  shows 


I 

II 

III 

To  tal 

Temperature 

375* 

600  * 

020  * 

620  * 

Time  in  hours 

3.75 

2.  5 

1.0 

7.3 

Total  gas 

2800 

3100 

900 

6800 

Gas  analysis: 

io 

I0 

I0 

f 

Ni  tro 

gen 

free  basis  - 

UO2 

13.  5 

20.  2 

4.8 

15.  4 

35.7 

34.0 

7.3 

29.8 

15.  5 

8.5 

6.7 

11.  1 

40.9 

14.  3 

9.9 

21.4 

^#4 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

h| 

2.7 

11.  3 

28.0 

10.0 

7.1 

19.0 

41.  3 

19.3 

00 

6.1 

7.7 

7.8 

7.2 

16.3 

12.9 

11.  5 

13.9 

CH4 

Trace 

9.3 

19.4 

6.8 

0.0 

15.6 

28.6 

13.  1 

^2^6 

Trace 

2.  5 

1.0 

1.3 

0.0 

4.  2 

1.4 

2.  5 

«2 

6 2.  2 

40. 5 

32.  3 

48.2 

c.o 

0.0 

0.0 

0.0 



. ^ 1 .I*'  . 


'•■t  -I 


(? 


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n 


ii/. 


illrJ 


76, 

TjflDie  XVlII. 

DATA  ON  FRACHONAL  CAFBONI ZATECN  FUN  # 10  ON  RESIDUE. 

Weight  of  charge  15.00  gnn. 

resictie  10.34  =69^ 

No  tar* 

lype  of  resi(3fcie:  Powder  like  original  chaise. 

Combined  data  on  run: 


'W.me 

Temp  erature 

Gas  Volume  Remarks 

0 *00" 

Room 

0 

15 

120 

100 

30 

160 

17  5 

45 

19  5 

220 

1 00 

225 

300 

Much 

more 

First  cut  - 

0 00 

225 

0 

45 

285 

400 

1 15 

370 

900 

Second  cut  - 

0 00 

370 

0 

30 

470 

500 

1 00 

48  5 

550 

1 15 

520 

600 

Third  cut  - 

0 00 

520 

0 

30 

570 

350 

35 

580 

425 

Last  ait  - 

Gas  Data: 

Fractions  or 

Ol  ts 

I II 

III 

IV 

To  tal 

Temperature 

225’  370' 

520  ’ 

560  ’ 

580  ' 

Time  in  hours 

1.0  1.25 

1.  25 

. 55 

4.0 

To  tal  g as 

300  900 

600 

425 

2225 

Gas  analysis: 

ic  $ 

1o 

1o 

iX)  p 

1.0  8.0 

14.0 

8.4 

8.8 

02 

20.0  16.8 

10. 5 

9.6 

14. 1 

C^4 

0.0  0.0 

0.0 

0.0 

0.0 

CeHe 

0.0  0.0 

0.0 

0.0 

0.0 

H2 

0.5  1.7 

9.5 

10.0 

5.  2 

uO 

0.5  2. 4 

17.0 

11.0 

7.9 

tfl4 

0.0  0.0 

0.0 

6.8 

1.3 

0^6 

0.0  0.0 

2.0 

5.8 

1.6 

N2 

78.0  71.1 

47.0 

47.8 

61. 1 

I 


*::3 


( ji'T 


('■u» 


4 


r • 


«U 


•J 


? 


• 'I 


.i 


77 


Taible  XrX, 

ijATA  ON  FRACnONiiL  CARBONIZATION  RJN  # 11  ON  RESIOJE. 


Weight  diarge 

15.00  gm. 

residiT  e 

10 . 42  " =69.5% 

No  tar. 

lype  of  residue:  Powder. 

Combined  data 

on  run : 

Time 

Tonp  eratu  re 

Gas  Volume 

0 ^00” 

Room 

0 

30 

IS  5 

130 

1 00 

280 

600 

2 00 

485 

1450 

First  cAt  - 

0 00 

48  5 

0 

45 

535 

350 

1 15 

565 

500 

Second  cut  - 

Gas  Data: 

Fractions 

I 

II 

To  tal 

Temperature 

48  5’ 

565’ 

565’ 

Time  in  hours 

2.0 

1.  25 

3.  25 

Total  gas 

1450 

500 

19  50 

Gas  analysis: 

% 

% 

% 

U)2 

17.0 

8.3 

14.9 

0 2 

13.6 

8.4 

12.  3 

H2 

6.5 

19.4 

9.9 

U) 

10.0 

30.0 

16.7 

tH4 

0.0 

10. 5 

2.7 

0.0 

1.8 

0.4 

N2 

52.9 

15.6 

43.1 

Nitrogen  free  basis 

OO2 

36  • 1 

9.9 

36. 2 

O2 

28.8 

9.9 

21.6 

^2 

13.8 

23. 1 

17.4 

xJO 

21.  3 

42.6 

29.4 

CH4 

0.0 

12.4 

4.7 

0.0 

2.  1 

.7 

N2 

0.0 

0.0 

0.0 

i- 


V 


■1,1 


V 


( 

■»i‘>»'lipi. -.. 

o” 

■ , ; , , ' — < < 


,'r.  f 


78 


Table  XX. 

DATA  ON  FRACTIONAL  CARBONIZATION  lUN  # 12  ON  RESIDUE. 


Weight  of  diarge  25.30  gnn. 

residue  16.25  " = 6 5% 

No  tar. 

l^pe  of  residue:  Powder. 

Combined  data  on  run? 

Time  Temperature  Gas  Volume 
0 ^00”  Room  0 

40  280  700 

Urst  cut  - 

0 00  280  0 

15  3?0  600 

Second  ait  - 

0 00  3?0  0 

50  500  900 

Third  cut  - 


0 00 

500 

0 

15 

510 

250 

7 20 

680 

2450 

Gas  Data: 

Fraction  s 

I 

II 

III 

IV 

To  tal 

Temperature 

280  ’ 

370  * 

500  ’ 

680  ’ 

680 

t 

Time  in  hours 

.75 

. 25 

.90 

8.  33 

9. 

2 

Total  gas 

700 

600 

900 

2450 

46  50 

Gas  analjfcsis: 

% 

% 

i 

% 

Nitrogoa  free 

U)2 

3.0 

8.2 

15.0 

6.0 

12.6 

18.4 

21.4 

7.7 

^2 

15.  3 

10. 3 

5.9 

2.  2 

6 4.  3 

23.  2 

8.3 

2.8 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

0.0 

H2 

2.0 

10.0 

9.3 

40.0 

8.4 

22.4 

13.3 

51.4 

CO 

3.  5 

16.0 

35.  2 

6.0 

14.7 

36.0 

50.4 

7.7 

Cfi. 

0.0 

0.0 

2.4 

21.  3 

0.0 

0.0' 

3.  3 

27,3 

0.0 

0.0 

2.4 

2.4 

0.0 

0.0 

3.  3 

3.1 

N2 

76.  2 

55.  5 

29.8 

22.  1 

0.0 

0.0 

0.0 

0.0 

4.  The  Effect  of  Selenium  oxychloride  Upon  the  Primary  Volatile 
Products  of  Coal: 

Four  fractional  carbonization  mns  were  made  upon  the  residue 
from  the  selenium  oxychloride  extraction  of  coal  in  exactly  tlie 
same  manner  as  upon  tlie  fresh  coal.  These  runs  were  numbered  9,10, 
11,  and  12,  Data  and  gas  analysis  for  these  runs  are  given  in  Tables 
XVII , XVIII , XTX,  and  XX.  Results  for  these  runs  were  plotted  in  purpl 
ink  upon  the  same  figures  III  to  XIV  inclusive  i^hidh  show  airves 


e 


V 


■‘.:  nr  A'  iv*' 

i ■ 


'in 


1 > 


79 


for  the  cai^oni zation  results  on  fresh  coal.  Corap arL sons  may  thus 
be  made  at  a glance. 

Gas  data  for  the  carbonization  run  on  the  residue  from  extrac- 
tion of  coal  ^vith  ^1  Qie-sel enium  o:^chloi'lde  mixture  were  also 
plotted  on  figures  III, IV,  and  V in  red  ink.  Comparative  results  of 
these  runs  with  those  on  fresh  coal  siiow  the  following; 

Coke  - Ihere  was  no  coke  residue  fomied  from  carbonization  of 
the  residues  from  the  seloiium  o^ chloride  extraction.  Hie  residues 
left  in  the  retort  were  all  powdery  and  had  the  same  appearance  as 
the  original  charge.  The  reag^t  entirely  destroyed  the  coking  pro- 
perty of  the  coal,  ei til er  through  extraction  of  the  bonding  material 
or  through  oxidation  of  the  cnal  mass.  The  average  percentage  of 
resi(iie  left  in  these  runs  was  67.90  ihicii  is  4.30^  less  than  the 
average  cx)ke  residue  from^  the  runs  on  fresh  cMial. 

Tar  - There  v;as  no  sign  of  tar  distilled  from  the  resiciies. 
Selaiium  oxychloride  removes  the  tar  forming  exmstituent  of  the  coal 
en  td  rely . 

Water  - Not  as  much  water  distilled  into  the  tar  trap  as  dur- 
ing carbonization  of  tlie  fre^i  cxial.The  temperature  of  heaviest 
distillation  of  w'ater  v/as  from  210’-  225 ’C.  naiidi  is  about  60 ’C. 
lower  than  tlie  average  maximuffi  distillation  point  for  water  of  dec- 
omposition of  the  c»al« 

lime  and  Temperature  - Figure  III  shows  thie  curve  for  Run  9 .i  ' 
with  a ivide  variation  from  Rins  10,11  and  12.  Run  9 was  the  only 
one  of  the  four  made  on  30  grams  of  residue.  Hie  others  being  mad.e 
on  less  residue  naturally  reached  a higher  temperature  in  the  same 
length  of  tirade.  Qirves  for  mns  6,7,8,  and  9 all  for  runs  in  \hich 
30  grams  of  charge  was  used,  siiov/s  that  thettemperature  increased 


80. 

with  the  time  approximately  tli  e same  en  coking  frecj:;  coal  and 
solvent  residue. 

Time  and  Gas  Volume  - Figure  IV,  shores  that  the  residue  whoi 
coked  under  the  same  conditions  gives  off  more  gas  in  any  certain 
1 eng  Hi  of  time  than  does  the  fresh  coal.  The  residue,  ^^i  cii  is  cellu- 
le sic,  is  practically  all  gas  foming  material,  and  also  there  is 
mudi  oJ^gen  present  in  tlie  residue,  'iitiich  accounts  for  the  rapid 
evolution  of  gas  and  the  large  volumes.  The  curve  for  Run  10  shov/s 
that  15  grams  of  residue  will  give  more  than  twice  as  much  gas  in  a 
certain  1 eng  Hi  of  time  than  an  eqiial  amount  of  the  fre^,  coal. 

Temperature  and  Volume  of  Gas  - Figure  V.  ^ows  Hi  at  the  runs 
oh  residue  numbered  10,11  and  12  yielded  more  gas  up  to  500’  than  dL< 
the  fresh  coal. 

Carbon  dioxide  - in  the  gas  from  Hie  residues  slioivs  a large 
increase  over  Hie  amount  givoi  off  by  the  coal.  This  may  iHiow  Hi  at 
the  residue  was  fairly  highly  oxidized,  by  a,ction  of  Hie  reagent,  and_ 
that  part  of  the  oiQrgen  was  chQnically  held,  or  that  Hie  residue 
being  mainly  cellulosic  in  nature  gives  lar^e  amounts  of  U)^  upon 
thermal  decomposition. 

0:j^gen  - The  residues  gave  off  mudli  more  oi^gen  than  the  freiHi 
coal.  This  would  point  to  the  fact  that  the  residues  absorbed  oxy- 
gen during  the  extraction  process  in  spite  of  precautions. 

Un  saturated  hyd^ro  carbons  and  Benzoie  - arc  absent  from  the  gas. 
The  reagent  entirely  removes  these  constitu^its  fi^oin  Hie  coal. 

Carbon  Monoxide  - is  present  in  mudi  larger  amounts  in  Hie  gas 
from  the  residues.  Decomposition  of  cellulo si c material  and  OO2 
would  account  for  this  increase. 


J 


81 


Paraffin  hydrocarbons  - Methane  and  etliane  occur  in  some\That 
smaller  amounts  in  gas  from  tlie  residues.  The  maximum  point  of 
tlieir  cli still aticn  is  readied  at  from  50  *-100'  higher  temperature 
than  from  distillation  of  coal.  It  seons  that  these  gases  are  two 
of  the  last  to  come  over  from  carbonization  of  the  residues  up  to 
6 25*0.  The  residue  ’ohidi  is  mainly  cellulosic  thus  yields  these 
saturated  hydrocarbons. 

Hydrogen-  shows  larger  percentages  at  lower  temperatures  than 
from  the  frei^  coal,  and  also  increases  more  gradually  so  that  at 
600*  slightly  less  hydrogen  is  evolved  from  the  residue  than  fi*om 
th  e CO  al . 

Vll.  Conclusions,  Part  II. 

Selenium  o5ydilorid.e  attadcs  coal  in  pi'nportion  to  the  amount 
of  resinic  volatile  or  tar  forming  content  of  the  coal.  Partially 
coked  coal  loses  little,  and  coke  nothing  upon  extraction.  The 
reagent  removes  tliose  resins  and  un  saturated  hydro  carbon  s rhidi 
form  the  tar  upon  distillation  of  coal.  The  extract  or  tar  m^aterlal 
is  not  separated  pure,  but  enters  into  a didnical  union  with  the 
reagent  forming  new  compounds. 

Selenium  oxy^diloride  reacts  more  completely  rvith  powdei’ed 
coal  with  the  evolution  of  heat.  The  action  is  not  a solvdit  one, 
but  a diemical  I’eaction.  All  resinic  and  tar  forming  material  of 
tlie  coal  is  removed,  and  changed  by  the  reagent.  The  cellulosic 
portion  of  the  coal  is  left  unharmed.  Selenium  oxychloride  removes 
a larger  portion  of  tlie  resinic  constituent  of  the  coal  than  do 
ordinary  organic  solvents. 

No  quantitative  extraction  is  possible.  A portion  of  the  rea- 
gent is  decomposed  resulting  in  the  deposition  of  red  seloiium 


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throughout  tl]  e extract  solution  said  residue.  The  residue  may  he 
purified  from  most  of  the  selenium,  hut  isolation  of  the  extract 
is  impossihle. 

Extraction  is  carried  out  to  tlie  hest  advantage  vd.thout  the 
use  of  external  heat.  Ordinary  solvent  extraction  methods  are  not 
applicable  to  tills  wort.  The  use  of  some  solvent  like  benzene  is 
necessary  to  aid  in  the  separation  of  the  residue. 

Selenium  and  chlorine  are  present  in  the  residue. 

The  ash  of  coal  does  not  seem  to  he  changed  to  any  marked 
extent  by  the  reagent.  Nitrogen  and  Sulfhr  do  not  ^ow  an  appreci«- 
able  diange.  It  should  not  he  concluded  from  this  that  the  nitrogen 
and  sulfLir  are  not  affected,  since  the  reagent  in  talcing  out  the 
resini c material  should  remove  some  of  these  t\7o  constituents. 

Paraffin  hydrocarbons  of  the  coal  ai-e  prohfUaly  not  attacked. 

The  residue  gives  off  much  moi'^e  oxygen  than  the  coal.  This  may 
he  due  to  oxidation  of  the  residue  and  absorption  of  much  o:?^gen 
wtiich  is  not  chemically  held. 

The  presence  of  0 3^gen  together  with  the  loss  of  resini c mat- 
erial of  the  coal  entirely  removes  the  coking  property  of  the  coal. 

Carbonization  of  coal  residues  after  extraction  vlth  selenium 
o^^diloride  shows  no  sign  of  tar  as  one  of  the  products  of  carbon - 
i zation. 

Seldiium.  oxydilorlde  divides  coal  into  a cellulosic  residue 
¥hi chyyiel ds  gas  chiefly,  and  a resini c portion  \hich  is  extracted 
and  vhich  contains  the  tar  foming  bodies.  The  resini c portion  also 
(X)n tributes  to  the  yield  of  gas  altho  in  not  quite  such  large  amount^ 
as  does  the  cellulosic  residue.  The  cellulosic  portion  begins  to 
decompose  upon  heating  before  the  resini c portion  has  reached,  a 


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8 3 


temperature  high  enough  to  decompose,  that  is,before  the  tar  and 
gas  yielded  from  tlie  resins  begins  to  distil*  Hie  formation  of  tar 
and  decomposition  of  the  resinic  material  in  coal  results  in  a 
rapid  increase  in  the  yield  of  gas,  and  if  at  tliis  time,  the  cellu- 
losic  portion  does  not  give  off  such  gases  as  00,002  and  O2  in  such 
quantities  as  to  prevent  bonding,  the  coal  mass  \vill  b^in  to  coke* 
Ihe  residual  cellulosic  portion  of  coal  upon  carbonization 
yields,  up  to  the  t^perature  of  secondary  decomposition,  as  much 
or  even  more  gas  tiian  did  the  original  coal  at  the  same  temperature* 
Hiis  gas  vhen  analyzed  shows  presjence  of  those  gases  rewriting  from 
decomposition  of  cellulose  plus  the  paraffin  hydro  caihons  and  large 
amounts  of  o3^gen*No  gas  of  an  un saturated  nature  or  those  formed 
from  them  are  present* 

^T!!!*  Summary* 

Selenium  oxychloride  attacks  finely  powdered  coal  \vith  the  evolu- 
tion of  heat*  Hie  amodnt  of  reaction  is  proportional  to  the 
volatile  content  of  the  coal*  U)ke  loses  no  tiling  by  attade* 
Selenium,  o^diloride  reacts  diemically  with  coal  and  thus  is  not  a 
true  solvent*  It  may  be  used  however  in  order  to  obtain  a 
residue* 

No  quantitative  extraction  is  possible  due  to  decomposition  of  the 
reagent  and  its  dionical  reaction  witli  the  tar* 

Neutral  solvents,  such  as  xyloie,  are  not  applicable  for  use  vdth 
sel  enium  o ly  chlo  ri de  in  co  al  extraction  wo  lic * 

Selenium  oiy  chlo  ride  divides  coal  into  two  main  portions,  the 
cellulosic  residue,  and  the  resinic  substances  ^hich  are 
extracted*  Hie  extracted,  material  consists  of  the  tar  forming 


4 V 


8 4. 

and  part  of  Uie  gas  yielding  constituent  of  tJie  coal  ;\tiidi  is 
resinic  o r "bi tumini c in  nature.  Hie  residue  consists  of  tbe  cellu- 
Icsic  portion  of  ISie  coal  together  vdth  the  ash  or  mineral  matter. 
This  cellulosic  residue  is  primarily  gas  fo  rming , yi  el  ding  such 
gases  as  carbon  monoxide,  carbon  dioxide,  hydrogen,o3g7^gen,  me  thane 
and  water  of  decomposition.  Ihe  extracted  constituent  reacts  ivith 
the  reagent  to  form  new  complex  compounds. 

Hie  residue  when  submitted  to  low  temperature  carbonization 
does  not  coke. 

No  tar  is  obtained  fmm  carbonization  of  the  residual  material. 
Selenium  oxychloride  removes  the  tar  entirely  from  the  cnal,  by 
extraction  of  the  tar  forming  constituents. 

Selenium  and  chlorine  are  present  in  the  residue  to  a small 
extoi  t. 

Hydrogen  of  cioal  is  given  off  in  largest  quantities  betireen 
350*  and  5?5’C  and  not  at  either  the  beginning  or  end  of  tlie  low 
temperature  period. 

Methane  is  given  off  by  distillation  of  the  cellulosic  con- 
stituent of  coal. 


8 5, 


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8G 


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